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Hubei Key Laboratory of Coal Conversion and New Material, Wuhan University of Science and Technology, Wuhan 430081, China
Department of Agriculture and Biological Engineering, Mississippi State University, Starkville, MS 39762, USA
c
Department of Bioengineering, University of Missouri, Columbia, MO 65211, USA
b
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 16 August 2013
Accepted 29 January 2014
Available online 2 April 2014
The syngas from biomass gasication may contain trace oxygen besides of gaseous hydrocarbons, which
will result in the temporarily or even permanently deactivation of FischerTropsch (FT) catalysts. In this
paper, CuOCeO2/Al2O3 catalyst was developed to efciently remove the trace oxygen from biomass
syngas. The experimental results demonstrated that CuOCeO2/Al2O3 catalyst was considerably effective
in removing oxygen to the level of below 1 ppm, its lifetime and deoxygenation capacity were 160 h and
3000 ml/g, respectively. Moreover, the optimum conditions of CuOCeO2/Al2O3 catalyst were 200 C,
3.45 105 Pa, and 3000 h1 gas hourly space velocity.
2014 Energy Institute. Published by Elsevier Ltd. All rights reserved.
Keywords:
Syngas
Oxygen
FischerTropsch
Removal
Deactivation catalyst
1. Introduction
The synthesis of transportation fuel has been the hot topic of biomass utilization due to the depletion of oil, national energy security and
environmental issues. At present, the most potential routes for producing transportation fuels from biomass is gasication, followed by
FischerTropsch (FT) synthesis [1]. However, the syngas from biomass gasication may contain some trace pollutants such as 10,000
15,000 ppm tars, 20004000 ppm ammonia, 100500 ppm H2S [2,3] and 0.11% oxygen [4,5] besides gaseous hydrocarbons. Unfortunately,
it has been discovered that trace oxygen can temporarily or even permanently deactivate the commercial FT catalysts. Yan et al. reported that
the lifetime of FT synthesis catalyst was only 40 h without the cleaning process. However, the lifetime of catalyst would be over 1000 h after
the oxygen in the syngas was removed to the level below 1 ppm, as shown in Fig. 1 [6].
It was reported that the catalyst oxidization by precious metals could remove oxygen to a level of below 0.02 ppm due to the reaction
between oxygen and hydrogen or carbon monoxide. The mechanism of the H2 oxidation reaction over Pt surface was studied by using mass
spectrometry and laser-induced uorescence [7]. Lei et al. pointed out that oxygen content in hydrogen could be reduced from 0.4% to
2 1063 106 (v/v) in the reaction temperature range of 150170 C with a space velocity of 5000 h1. Meanwhile, the increase reaction
temperature had little inuence on the removal efciency of oxygen [8]. However, the widely application of removing oxygen from the
syngas was suppressed because of the high cost of noble metals and sulfur poisoning.
CuO is a cheap catalyst with high activity, which has been also widely used in a variety of catalytic reactions including the oxidation of carbon
monoxide and hydrocarbons [9]. Avgourpoulos et al. reported that CuOCeO2 catalyst had the same activity as Pt/Al2O3 catalyst [10]. Wan et al.
pointed out that Cu species were active phase after the pretreatment by CO [11]. In the presence of rich hydrogen, hydrogen molecules were
rstly absorbed on the catalyst surface, followed by disassociating from the catalyst surface and forming hydrogen atoms. At the same time,
oxygen also reacted with catalyst and formed the oxides of O2. Lastly, hydrogen atoms easily reacted with O2 and formed water [11].
In the system of rich CO, the reaction complies with the LangmuirHinshelwood mechanism [12]. During catalytic processes, the adsorbed
oxygen reacts with carbon monoxide, which results in forming a CO3 complex as an intermediate stage. The reaction releases much heat and
leads to the sharply increase of temperature. The high temperature may change the crystal and pore structure of the deoxidant catalyst, which
may lead lower the dispersion caused by the sintering. Zhu [13] and Zeng [14] stated that Au/CeO2 and CuO/CeO2 catalyst had a strongly active for
CO oxidation due to their oxygen storage capacity. BASF also proved that CuO catalyst tablets could remove oxygen or CO/H2 from gas stream [15].
* Corresponding author.
E-mail address: fyu@abe.msstate.edu (F. Yu).
http://dx.doi.org/10.1016/j.joei.2014.03.005
1743-9671/ 2014 Energy Institute. Published by Elsevier Ltd. All rights reserved.
247
Fig. 1. Comparison of the catalyst lifetime with and without clean process.
Table 1
The compositions of catalyst.
Name
Ce (wt %)
Cu (wt %)
Al2O3 (wt %)
Catalyst F
Catalyst P
5
0
10
10
85
90
Ge prepared MnCuCo/montmorillonite deoxidant by co-precipitation, which could reduce oxygen content from 500 106 to
0.01 106 (v/v) at a space velocity of 10008000 h1, and the operation temperature range of 25200 C [16]. Ren et al. also developed a
MnCuCo/active carbon deoxidant which had a high selectivity of conversing CO to CO2. After the clean process, the oxygen concentration
was below 1 ppm [17].
In this paper, copper catalysts with CeO2 promoter and alumina support were developed. The optimum operations and their catalyst
performances were also investigated.
2. Experimental
2.1. Material and method
It was discovered that the oxides of transition metals combined with other oxides such as cerium had the active radicals hydroxyl roots,
which could store oxygen in its structure. Moreover, Ceria could promote the dispersion of copper on alumina support [18]. Therefore, the
activity of catalyst was increased when CeO2 was incorporated into CuO lattice. In this experiment, CeO2 and alumina were used as promoter
and support, respectively. According to the experimental results of Strohmeier [19], the highly dispersed Cu oxide species were well
interacted with support alumina when Cu content in the catalyst was 10%wt. Three catalysts with different components were prepared, and
the compositions are listed in Table 1.
The catalysts were prepared by a two-step impregnation method. As for catalyst F, the required amount of cerium nitrate [Ce(NO3)3$6H2O] (99.5%, Acros Organics) solution was rstly impregnated over the g-alumina (surface area, 246 m2/g, pore volume, 1.15 mL/g),
then the precursor was dried at 120 C for 6 h, followed by calcinated at 600 C for 6 h. Thus, CeO2/Al2O3 was prepared.
During the subsequent impregnation, the required amount of copper nitrate [Cu(NO3)2$3H2O] (99.7%, SigmaAldrich) solution was
impregnated over the prepared CeO2/Al2O3 and dried under 120 C for 6 h, followed by calcinations under 350 C for 6 h. The nal catalyst
was prepared. The properties of the catalysts were listed in Table 2.
2.2. Pretreatment
The reduction can activate surface copper oxide into metal copper, which increases the catalyst activity and its oxygen capacity. Wan et al.
[11] demonstrated that the deoxygenation efciency of the CO-pretreated catalyst was higher than that of fresh catalysts. In these runs, catalyst F
was active by CON2 stream (20% CO by volume, N2 was balanced gas) at 250 C for 6 h under atmosphere pressure. During the reduced process,
the gas ow rate was kept about 20 ml/min. After the reduction, the reactor was purged with N2 stream until the treated catalyst was cooled to a
determined temperature. Lastly, the catalyst was directly exposed to the syngas when the reactor temperature was stabilized.
Table 2
The properties of the catalyst.
Name
Catalyst F
Catalyst P
129
187
0.31
0.64
4.7
7.5
248
CO2
Xin Xout
Xout
100% 1
Xin
Xin
(1)
where C is the conversion rate (%) and X is the (inlet or outlet) oxygen concentration (ppm).
In Eq. (2), the deoxygenation capacity (DC) is the total amount of syngas cleaned that the residual oxygen concentration is below 1 106
(v/v) every g catalyst.
Deoxygenation capacityml=g
Fig. 3. TG/DTG of (a) and (b) as a function of temperature. (a) P and (b) F.
(2)
249
(3)
(4)
C O2 /CO2
DH 405:9 kJ=mol
(5)
250
1
H2 O2 /H 2 O
2
DH 242 kJ=mol
(6)
According to Eqs. (5) and (6), the maximum consumption of H2 was about 1.8% if oxygen was completely removed (the oxygen concentration in syngas was 0.9%). However, Fig. 5a presented that the variation of H2 concentration was only about 1%. Hence, it can be
concluded that there was limited CO2 formation during the oxygen reduction, which was proven by Fig. 5b. Park et al. stated that the CO
Fig. 6. Effect of gas hourly space velocity (GSHV) on deoxygenation efciency at 150, 180 and 200 C, 0 Pa over catalyst F.
251
Fig. 7. Effect of temperature on F at 170 C and 200 C, 3.45 105 Pa, and gas hourly space velocity is 3500 h1.
oxidation activity decreased with increasing CO2 content due to the competitive adsorption of CO and CO2 on the ceria surface and carbonate
formation, which prevented the participation of oxygen [22]. In order to decrease copper carbonate, they declared that the reaction
temperature should be above 180 C.
Fig. 5 also presented that the maximum consumption of H2 occurred at 3.45 105 Pa and 100 C when catalyst F was used as catalyst.
Moreover, it was also found that the increase of pressure could promote the consumption of H2 during the oxygen catalytic removal.
However, the consumption of CO seemed to be independent of the reaction temperature. At the same time, the increase of reaction pressure
had a minor negative inuence on CO oxidation reaction.
4. Conclusions
The syngas from biomass gasication may contain some trace pollutants such as 10,00015,000 ppm tars, 20004000 ppm ammonia,
100500 ppm H2S and 0.11% oxygen, besides of gaseous hydrocarbons. Unfortunately, it has been discovered that trace oxygen can
temporarily or even permanently deactivate the commercially FT catalysts.
In order to remove oxygen from syngas to 1 ppm, copper catalyst was developed in this paper. The experimental results discovers that
copper is an effective catalyst for removing oxygen from syngas, and its lifetime and deoxygenation capacity are 160 h and 3000 ml/g,
respectively. The optimum conditions of copper catalyst are 200 C, 3.45 105 Pa, and 3000 h1 gas hourly space velocity.
Acknowledgement
Funding for this work was provided by the U.S. Department of Energy under Grant DOEDE-FG36-06GO86025 and DE-FC2608NT01923,
and the U.S. Department of Agriculture under Award (AB567370MSU).
252
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