Energy & Fuels 2005, 19, 305-310 305

Characteristics of the Synthesis of Methanol Using

Biomass-Derived Syngas
Xiuli Yin and Dennis Y. C. Leung*
Department of Mechanical Engineering, The University of Hong Kong,
Pokfulam Road, Hong Kong

Jie Chang, Junfeng Wang, Yan Fu, and Chuangzhi Wu

Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, 1 Nengyuan Road,
Wushan, Tianhe District, Guangzhou, 510640, China

Received June 11, 2004. Revised Manuscript Received October 6, 2004

The characteristics of methanol synthesis from biomass-derived syngas were studied in a high-
pressure microreactor with a commercial Cu/ZnO/Al2O3 catalyst. A series of experiments was
conducted at a temperature range of 215-270 °C, with three different pressures of 2.6, 3.6, and
4.6 MPa and space velocities of 4000-12 000 h-1. Four model bio-syngases with different H2/
CO/CO2/N2 ratios, which were configured according to the results of biomass gasification, were
used in the studies. The effect of temperature, pressure, and space velocity on the space-time
yield and selectivity of methanol was explored. The sensitivity analysis of the yield and selectivity
of methanol with different H2/(CO + CO2) and CO2/CO ratios was investigated. Results show
that both yield and selectivity of methanol are affected by the operating parameters, and optimum
conditions exist within the tested range. The yield of methanol is sensitive to the H2/(CO + CO2)
ratio, whereas the selectivity of methanol is more sensitive to the CO2/CO ratio. It is concluded
that the yield of methanol from the syngas derived from air-steam gasification is lower than
that from catalytic gasification, whereas the selectivity of methanol is the reverse. With a partial
removal of CO2, both yield and selectivity of methanol can be improved.

Introduction The latter consists mainly of H2 and CO, with a small

amount of CO2,10 whereas bio-syngas consists much
The use of biomass as an energy resource has received more of CO2 but much less of H2, resulting in a low H/C
much attention recently, because of its ability to provide ratio and a high CO2/CO ratio. Therefore, the composi-
additional energy and, at the same time, reduce green- tion of bio-syngas is not favorable for methanol synthesis
house gas emissions. Methanol synthesis via biomass under the conventional method.
gasification has already been suggested as an environ-
The composition of bio-syngas is dependent on the
mentally friendly method of biomass utilization.1-6
gasification method used. Theoretically, a syngas with
Several biomass-to-methanol demonstration projects
a H2/CO ratio of 2.0, which is appropriate for methanol
have been developed recently, such as the Hynol project
synthesis, can be obtained adiabatically by adjusting
in the United States, the BioMeet and Bio-Fuels projects
certain gasification parameters.11 However, the differ-
in Sweden, and the BGMSS project in Japan.7-9
ences between the actual data and theoretical results
The composition of syngas derived from biomass is are substantial. Moreover, economical aspects must be
different from that derived from natural gas and coal. considered for practical processes. In most cases, bio-
syngas is a CO2-rich and H2-deficient feed gas, which
* Author to whom correspondence should be addressed. Tel: +852-
28597911. Fax: +852-28585415. E-mail: [email protected]. can be tailored in the downstream process by water-
(1) Bridgwater, A. V.; Double, J. M. Fuel 1991, 70 (10), 1209-1224. gas shift reaction, by methane reforming, by CO2
(2) Dong, Y.; Steinberg, M. Int. J. Hydrogen Energy 1997, 22 (10- removal, or by supplying H212 to readjust its composition
11), 971-977.
(3) Hamelinck, C. N.; Faaij, A. P. C. J. Power Sources 2002, 111 before entering into the synthesis loop. However, the
(1), 1-22. capital cost for syngas generation made in this way will
(4) Chmielniak, T.; Sciazko, M. Appl. Energy 2003, 74 (3-4), 393-
403. be very high. Therefore, simplification in the syngas
(5) Kaneko, S.; Kobayashi, Y.; Kabata, T.; Aruga, T. U. S. Patent production would improve the overall process economics
No. US2002/0087037A1, July 4, 2002. significantly.
(6) Beenackers, A. A. C. M.; Van Swaaij, W. P. M. Int. J. Solar
Energy 1984, 2 (5), 349-367.
(7) Norbeck, J. M.; Johnson, K. http://www.methanol.org/pdf/ (10) Wu, J.; Saito, M.; Takeuchi, M.; Watanabe, T. Appl. Catal., A
Hynolexec.pdf, 2000. 2001, 218 (1-2), 235-240.
(8) Brandberg, Å. R. L.; Ekbom, T. http://www.ecotraffic.se/pdf/ (11) Kinoshita, C. M.; Wang, Y.; Takahashi, P. K. Energy Sources
isafxii.pdf. 1991, 13 (3), 361-368.
(9) Mitsubishi Heavy Industries, http://www.mhi.co.jp/power/e_power/ (12) Jun, K.-W.; Roh, H.-S.; Kim, K.-S.; Ryu, J.-S.; Lee, K.-W. Appl.
techno/biomass/, 2003. Catal., A 2004, 259 (2), 221-226.

10.1021/ef0498622 CCC: $30.25 © 2005 American Chemical Society

Published on Web 11/20/2004
306 Energy & Fuels, Vol. 19, No. 1, 2005 Yin et al.

Table 1. Composition of Syngases and Their H2/(CO + CO2) and CO2/CO Ratios
syngas H2/CO/CO2/N2 H2/(CO + CO2) CO2/CO remark
1 39.9/35.2/19.9/5.0 0.7 0.56 low H/C ratio; represents air-steam gasification
2 50.1/24.9/19.9/5.1 1.1 0.8 medium H/C ratio, medium CO2/CO ratio; represents catalytic gasification
using an air-steam gasification agency
3 66.2/26.8/3.1/3.9 2.2 0.1 high H/C ratio, low CO2 content; represents catalytic gasification with
partial removal of CO2 (or a conventional syngas)
4 50.7/21.5/22.8/5.0 1.1 1.1 medium H/C ratio, high CO2/CO ratio; represents catalytic gasification
using an air-steam gasification agency

A new possible way of methanol synthesis is to mass,18-20 and related results were analyzed in the work by
convert bio-syngas directly to methanol, according to a Yin.20 Different gasification methods can produce syngas with
once through methanol (OTM) concept. With this con- different compositions. These process routes exhibit varying
cept, inexpensive biomass syngas can be directly syn- efficiencies, as well as capital and operating complexities. Note
thesized to methanol, because the syngas adjustment that a suitable method would be dependent on specific project
step, which is adopted in traditional way, can be and/or site-specific circumstances. In this paper, gaseous
products derived from air-steam gasification and catalytic
omitted, thus greatly reducing the cost of syngas
gasification using air-steam as the agency were configured
production. The total efficiency of the system can be
as model syngases for methanol synthesis. As known, gasifica-
improved by combining heat and power generation. In tion produces a gaseous product that contains H2, CO, CO2,
such case, however, water would be produced, along N2, CH4 and CnHm, etc. CH4 and CnHm can be considered to be
with methanol, during the synthesis process, which inert gases that have passed through the methanol synthesis
could accelerate the crystallization of copper and ZnO reactor with unchanged composition but can be utilized in the
and lead to deactivation of the catalyst.10 Based on the downstream process to supply heat or power, as in the OTM
previous studies on methanol synthesis from CO2 hy- concept. The existence of a large amount of inert gases in the
drogenation,10,13,14 it was possible to assume that the syngas decreases the effective partial pressure of H2 and CO.
Cu/ZnO-based catalysts could be active and stable for To simplify the methanol synthesis process, the model syn-
a long period in a continuous methanol synthesis gases were made, consisting only of H2, CO, CO2, and a small
operation from CO2-rich syngas with the development amount of N2. N2 acts as a balance gas for the calculation of
of catalyst for CO2 hydrogenation. On the other hand, mass balance, because N2 is neither consumed nor produced
with the development of liquid-phase methanol synthe- under the reaction conditions. The air-steam gasification
sis technology,15-17 the reactor can operate at a wide produced a feed gas with a H2/(CO + CO2) ratio of 0.7 and a
range of H2/(CO + CO2) ratios and without any catalyst CO2/CO ratio of 0.56 at a temperature of T ) 900 °C, steam to
biomass weight ratio (S/B) of 2.7, and equivalence ratio (ER)
deactivation, even at low H/C ratios. This makes the
of 0.22. Thus, syngas 1, which represents the air-steam
biomass-derived syngas suitable for methanol synthesis.
gasification conditions, was referenced as a low H/C ratio
The two previously mentioned aspects, together with the syngas. Catalytic gasification produced various feed gases with
advancement in biomass gasification technology, open different H2/CO and CO2/CO ratios, depending on the catalyst
up great research opportunities for methanol synthesis used and operating conditions; thus, it is difficult to identify
via biomass gasification. a model syngas that can represent this gasification method
Methanol synthesis directly from bio-syngas has exclusively. In the present study, two syngases with similar
recently attracted much interest; however, there is only H2 content but different CO2/CO ratios were configured as
a small amount of literature aimed at investigating the syngas 2 and syngas 4, which represent medium H/C ratio
characteristic of methanol synthesis using bio-syngas. syngas, with medium CO2/CO and high CO2/CO ratio, respec-
In this paper, we try to investigate the effect of the tively. With a partial removal of CO2, the ratios of H2/(CO +
operation parameters (i.e., temperature, pressure, space CO2) and CO2/CO in the feed gas can be changed greatly, which
velocity) on the space time yield (STY) and selectivity may strongly affect the result of methanol synthesis. Syngas
3, was configured as a H2-rich syngas, and its composition is
of methanol, with the use of a commercial Cu/ZnO/Al2O3
similar to that of conventional syngas. The characteristics of
catalyst. Sensitivity analysis of the yield and selectivity
the four model syngases are listed in Table 1.
of methanol that was related to the H2/(CO + CO2) and
Apparatus and Catalyst Used. The catalyst used in this
CO2/CO ratios was also studied. The purpose of the
experiment, with a molar ratio of 2:1 for copper and zinc, was
present study is not only to study the characteristic of
a commercial Cu/ZnO/Al2O3 catalyst for methanol synthesis.
CO/CO2 hydrogenation, but also to explore an economic
The catalyst was packed into a high-pressure microreactor and
way to produce methanol from biomass. reduced in a gas mixture of H2 (5%) and N2 (95%) at a space
velocity of SV ) 5000 h-1 and a pressure of P ) 2 MPa. Details
Experimental Details of the microreactor are described elsewhere.20 Methanol
synthesis reaction was then performed over the catalyst in a
Preparation of Syngas. The composition of syngases used temperature range of 215-270 °C, at three different pressures
in this experiment was configured according to the result of (i.e., 2.6, 3.6, and 4.6 MPa) and at space velocities of SV )
air-steam gasification and catalytic gasification with bio- 4000-12 000 h-1.

(13) Saito, M.; Fujitani, T.; Takeuchi, M.; Watanabe, T. Appl. Catal., (17) Setinc, M.; Levec, J. Chem. Eng. Sci. 1999, 54 (15-16), 3577-
A 1996, 138 (2), 311-318. 3586.
(14) Saito, M.; Takeuchi, M.; Watanabe, T.; Toyir, J.; Luo, S.; Wu, (18) Lv, P. M., Chang, J., Wang, T. J., Fu, Y., Chen, Y.; Zhu, J. X.
J. Energy Convers. Manage. 1997, 38, S403-S408. Energy Fuels 2004, 18 (1), 228-233.
(15) Tjandra, S.; Anthony, R. G.; Akgerman, A. Ind. Eng. Chem. Res. (19) Lv, P. M.; Chang, J.; Xiong, Z. H.; Huang, H. T.; Wu, C. Z.;
1993, 32 (11), 2606-2607. Chen, Y.; Zhu, J. X. Energy Fuels 2003, 17 (3), 677-682.
(16) Pass, G. G.; Holzhauser, C.; Akgerman, A.; Anthony, R. G. (20) Yin, X. L. Study on the Synthesis of Methanol from Biomass-
AIChE J. 1990, 36, 1054-1060. Derived Syngas, Ph.D. Thesis, The University of Hong Kong, 2004.
Synthesis of Methanol Using Biomass-Derived Syngas Energy & Fuels, Vol. 19, No. 1, 2005 307

has a high H/C ratio and low CO2 level. The maximum
yield can be observed to be dependent on the gas
composition. The yield for syngas 1 and syngas 2 are
less than that of syngas 3, within the tested range;
however, the differences are different at different tem-
peratures. For syngas 1, the difference at lower tem-
perature range is smaller than that at higher temper-
ature range. The differences vary from 27% to 53%. For
syngas 2, the yields are very similar to that of syngas 3
for T ) 245-260 °C, with a decrement of 4%-5%.
Comparison of syngas 1 and syngas 2 shows that the
yield of methanol for syngas 1 is less than that for
syngas 2, by ∼11%-49% within the tested range. The
difference between the three syngases is mainly caused
by their difference in the H2/(CO + CO2) and CO2/CO
Figure 1. Space-time yield of methanol, as a function of
temperature at a pressure of P ) 3.6 MPa and space velocity ratios.
of SV ) 7000 h-1. Figure 2 shows that the selectivity of methanol for
both syngas 1 and syngas 3 decreases as the tempera-
ture increases, whereas that of syngas 2 increases as
the temperature increases up to ∼245 °C and then
decreases thereafter. However, the selectivity of water
shows the opposite trend as that of the methanol, with
a minimum at ∼250 °C. The selectivity of methanol for
syngas 1 and syngas 2 are less than that of syngas 3,
with a decrement of 0.6%-2% for syngas 1 and 2%-5%
for syngas 2. The selectivity for syngas 1 is ∼1%-5%
higher than that of syngas 2, despite the fact that its
H/C ratio is lower than the latter. The selectivity of
methanol seems more related to the CO2/CO ratio than
that of the H2/(CO + CO2) ratio.
The heat of reaction of methanol synthesis from CO2
hydrogenation is 60% of that from CO hydrogenation;
therefore, the reaction from the former can be operated
Figure 2. Selectivity of methanol and H2O, as a function of at a lower temperature than the latter. It has been
temperature, at P ) 3.6 MPa and SV ) 7000 h-1. observed that methanol can be produced more rapidly
at a lower temperature with CO2 than with CO.22 The
Results and Discussions reaction rate of CO hydrogenation increases as the
temperature increases, up to a certain value, causing
Effect of Temperature. The effect of operating the change in selectivity. This may be one of the reasons
temperature on the yield and selectivity of methanol why the selectivity of methanol increases as the tem-
was investigated in the range of 210-270 °C with a perature increases, up to an optimum temperature for
fixed pressure of P ) 3.6 MPa and a space velocity of syngas 2. At higher temperature, the reactions are
SV ) 7000 h-1. Syngases 1, 2, and 3 were used for the controlled by the thermodynamics; the hydrogenation
test. Figure 1 presents the yield of methanol, as a of CO2 is more significant than that of CO, causing the
function of temperature, whereas Figure 2 shows the decrease in the selectivity of methanol beyond the
selectivity of methanol and water, as a function of optimum temperature.
temperature, for different syngases. Effect of Pressure. The effect of operating pressure
As shown in Figure 1, the yield of methanol for the on the yield and selectivity of methanol was investigated
three syngases increases as the temperature increases, in the pressure range of 2.6-4.6 MPa with T ) 250 °C
reaches its maximum yield at ∼250 °C, and then and SV ) 7000 h-1, using syngas 2. Figures 3 and 4
decreases thereafter. The presence of a maximum yield show the yield and selectivity of methanol, respectively,
of methanol indicates the shifting from kinetics-limited as a function of operation pressure.
to thermodynamics-limited reactions. It is well-known From the molar analysis, the reactions of methanol
that the reaction rate of CO/CO2 hydrogenation always synthesis results in a decrease in gas volume, thus
increases as the temperature increases.21 However, reducing pressure. Therefore, the expected increase in
because it is an exothermic reversible reaction, the yield methanol yield with increasing pressure can be observed
of methanol will be controlled by both kinetics and in Figure 3. Figure 4 shows that the selectivity of
thermodynamics. Its equilibrium constant decreases as methanol increases as the pressure increases, whereas
the temperature increases, so the yield of methanol is the selectivity of water has the opposite trend. These
reduced beyond the optimum temperature. The change results indicate that high pressure does not favor the
in the yield of methanol with temperature for syngas 1 conversion of CO2, which is consistent with the predic-
and syngas 2 shows a similar trend as syngas 3, which tion from chemical equilibrium calculation.20

(21) Liu, X.-M.; Lu, G. Q.; Yan, Z.-F.; Beltramini, J. Ind. Eng. Chem. (22) Thivolle-Cazat, J.; Bardet, R.; Trambouze, Y. Prepr. Symp.s
Res. 2003, 42 (25), 6518-6530. Am. Chem. Soc., Div. Fuel Chem. 1984, 29 (5), 189.
308 Energy & Fuels, Vol. 19, No. 1, 2005 Yin et al.

Figure 3. Yield of methanol, as a function of pressure, at T Figure 6. Selectivity of methanol and H2O, as a function of
) 250 °C and SV ) 7000 h-1 for syngas 2. space velocity (SV), for syngas 2 at P ) 3.6 MPa and T ) 240
°C.

Figure 6, the selectivity of methanol decreases slightly

as SV increases but vice versa for water. This is because
the effect of SV on the selectivity of methanol is related
to both CO and CO2 hydrogenation when bio-syngas is
used. At high SV values, the conversion of CO2 is more
significant than that of CO, as confirmed by Sizgek et
al.24 and Zhang et al.25 Another reason may be due to
the fact that the adsorptivity of CO2 on a copper-based
catalyst is greater than that of CO.26 The desorption of
CO was accelerated as the SV value increased, causing
a decrease in methanol selectivity and an increase in
water selectivity. It can be concluded that SV has
different effects on the selectivity for different reactant
Figure 4. Selectivity of methanol and H2O, as a function of
pressure, at T ) 250°C and SV ) 7000 h-1 for syngas 2. gases, which is consistent with the result of Lee et al.27
For the present case of bio-syngas with high CO2
content, an increase in the SV value causes a slight
decrease in the selectivity of methanol.
Sensitivity Analysis Related to H2/(CO + CO2)
and CO2/CO Ratios. To investigate the effect of H2/
(CO + CO2) and CO2/CO ratio on the yield and selectiv-
ity of methanol, experiments were performed at three
different temperatures (i.e., 240, 250, and 260 °C), with
SV ) 7000 h-1 at a pressure of P ) 3.6 MPa. All the
syngases (i.e., syngases 1, 2, 3, and 4) were used for this
investigation. As shown in Table 1, the H2/(CO + CO2)
ratio for the four syngases were 0.7, 1.1, 2.2, and 1.1,
respectively, and the corresponding CO2/CO ratios were
0.56, 0.8, 0.1, and 1.1, respectively. Figures 7 and 8 show
Figure 5. Yield of methanol, as a function of space velocity the relationship between yield and selectivity of metha-
(SV), for syngas 2 at P ) 3.6 MPa and T ) 240 °C. nol and the ratios of CO2/CO and H2/(CO + CO2),
respectively.
Effect of Space Velocity. Space velocity (SV) is Figure 7 shows that the yield of methanol does not
another important factor that affects the methanol exhibit a monotonic trend with an increase in CO2/CO
synthesis reaction. Generally, the rate of CO and CO2 ratio, whereas the yield increases with the ratio of H2/
conversion decreases as SV increases; however, the yield (CO + CO2) increasing from 0.7 to 2.2. However, the
of methanol and turnover frequency of methanol forma- selectivity of methanol does not show a similar trend.
tion increases as SV increases.23 In this regard, the Figure 8 indicates that the selectivity of methanol
effect of SV on the yield and selectivity of methanol has decreases as the CO2/CO ratio increases, within the
been investigated for SV ) 4000-12 000 h-1 with T ) tested CO2/CO and temperature. Syngas 3, which has
240°C and P ) 3.6 MPa. Syngas 2 was used for this low CO2/CO ratio of 0.1, shows the highest selectivity
study. Figures 5 and 6 show the yield and selectivity of of methanol. It can be observed from gas chromatogra-
methanol, as a function of SV. phy (GC) analysis that methanol is the main product
As can be observed from Figure 5, the yields of both
(24) Sizgek, G. D.; Curry-Hyde, H. E.; Wainwright, M. S. Appl.
methanol and total liquid product increase as SV Catal., A 1994, 115 (1), 15-28.
increases. The percentage of methanol is ∼95% of the (25) Zhang, Y.; Sun, Q.; Deng, J.; Wu, D.; Chen, S. Appl. Catal., A
1997, 158 (1-2), 105-120.
total liquid product, over the tested range. As shown in (26) Cai, Q. R.; Peng, S. Y. Catalytic Function in C1 Chemistry;
Chemical Industry Publishing Company: Beijing, 1995; pp 153-166.
(23) Sun, Q.; Zhang, Y.-L.; Chen, H.-Y.; Deng, J.-F.; Wu, D.; Chen, (27) Lee, J. S.; Lee, K. H.; Lee, S. Y.; Kim, Y. G. J. Catal. 1993, 144
S.-Y. J. Catal. 1997, 167 (1), 92-105. (2), 414-424.
Synthesis of Methanol Using Biomass-Derived Syngas Energy & Fuels, Vol. 19, No. 1, 2005 309

Their results were not completely consistent with each

other, because of the different catalysts and reaction
conditions used. Both H2/(CO + CO2) and CO2/CO ratio
affect the yield and selectivity of methanol; however, it
maybe deduced that the yield of methanol is sensitive
to the former ratio than the latter, but vice versa for
the selectivity of methanol.
Characteristics of Methanol Synthesis from Bio-
mass-Derived Syngas. The process of methanol syn-
thesis from biomass-derived syngas involves the follow-
ing three main reactions:29

CO + 2H2 ) CH3OH (∆H ) -90 kJ/mol) (1)

CO2 + 3H2 ) CH3OH + H2O
Figure 7. Relationships between yield of methanol and the (∆H ) -53.66 kJ/mol) (2)
CO2/CO and H2/(CO + CO2) ratios at T ) 240, 250, and 260
°C, P ) 3.6 MPa, and SV ) 7000 h-1. R represents the H2/(CO CO2 + H2 ) CO + H2O (∆H ) +36.9 kJ/mol) (3)
+ CO2) ratio.
As indicated by Li et al.,30 the selectivity of methanol
is <45% from CO2 hydrogenation with a copper-based
catalyst. It is because a copper-based catalyst can
intensively adsorb CO2, which facilitates the competitive
reaction between reactions 2 and 3; hence, the selectivity
of methanol from CO2 hydrogenation is less than that
of CO. It can be found that CO2 hydrogenation produces
some amount of water, which not only deactivates the
catalyst but also increases the burden due to the need
to separate the water from the methanol produced.
From the chemical balance, the H2/CH3OH ratio is 2
and 3 in reactions 1 and 2, respectively; thus, CO2
hydrogenation consumes 0.7 Nm3 of H2 more than CO
to produce 1 kg of methanol. The methanol synthesis
Figure 8. Relationships between the selectivity of methanol
and the CO2/CO ratio at T ) 240, 250, and 260 °C, P ) 3.6 from bio-syngas consists of both CO and CO2 hydroge-
MPa, and SV ) 7000 h-1. nation; CO and CO2 are competitively adsorbed onto the
surface of the catalyst, so reaction 3 will be restrained,
and only a minor amount of water was formed as a side and the selectivity of methanol will be increased ac-
product for this syngas. The selectivity of methanol for cordingly.
syngas 1 is higher than that of syngas 2, despite its low The conversion rate of CO and CO2 is dependent on
H2/(CO+CO2) ratio, because the former syngas has a the reaction conditions, such as temperature, pressure,
smaller CO2/CO ratio than the latter. Syngas 4 has a space velocity, and CO2/CO ratio. As discussed previ-
H2/(CO + CO2) ratio similar to that of syngas 2, but a ously, there are optimum conditions for the hydrogena-
higher CO2/CO ratio (>1), which leads to the rapid tion of CO/CO2, at which the selectivity of methanol is
decrease in selectivity of methanol, as shown in Figure higher. The CO2 conversion rate exhibits an increasing
8. Correspondingly, the yield of methanol only shows a behavior with increasing CO2/CO ratio. The beneficial
slightly decrease for syngas 4 (see Figure 7). The result effect of the presence of CO2 up to a certain level has
indicates that, when the concentration of CO2 exceeds been proven;24 however, at very high CO2 concentra-
that of CO, the conversion rate of CO2 increases greatly tions, an inhibiting effect is quite evident. In this study,
as the concentration of CO2 increases, so the selectivity it can be found that, when the CO2/CO ratio is >1, the
of methanol decreases rapidly. This happens because selectivity of methanol is rapidly decreased.
CO and CO2 is competitively adsorbed onto the surface For the case of bio-syngas directly used for synthesis
of catalyst, active position of CO2 hydrogenation oc- of methanol, the CO2/CO ratio is determined by the
cupied by CO can be partly converted to CO2, which then gasification process and feedstock. In most cases, the
decreases the selectivity of methanol. CO2 concentration in bio-syngas is high with a low H2/
Note that one of the ratios of CO2/CO and H2/(CO + (CO + CO2) ratio; thus, it is important to utilize the H2
CO2) could not be maintained at constant values while effectively (in other words, improve the CO hydrogena-
varying the other, because the four syngases used were tion), for the purpose of improving the yield of the target
configured according to the experimental result of product (methanol). It can be controlled by optimizing
biomass gasification. The syngas possesses a typical the reaction conditions. The following conditions should
composition, representing different production and treat- be taken into account:
ment processes, and their H2/(CO + CO2) and CO2/CO (28) Sahibzada, M.; Metcalfe, I. S.; Chadwick, D. J. Catal. 1998,
ratios lie within a limited range. The increase in yield 174 (2), 111-118.
with increasing H2/(CO + CO2) ratio has been proven (29) Lee S. Methanol Synthesis Technology; CRC Press: Boca Raton,
FL, 1990; p 25.
by Tjandra et al.15 The effect of the CO2/CO ratio on (30) Li, J.; Zhang, W.; Au, C. T. J. Mol. Catal. (China) 1998, 12 (3),
the yield of methanol has been studied elsewhere.24,28 189-192.
310 Energy & Fuels, Vol. 19, No. 1, 2005 Yin et al.

(1) The temperature should be controlled within a (2) The yield and selectivity of methanol from bio-
suitable range, to keep a higher yield and selectivity of syngas are less than those from conventional syngas.
methanol. The decrement is dependent on the composition of the
(2) Higher pressure can increase the yield and selec- bio-syngas. The yield of methanol from syngas with a
tivity of methanol. However, considering the cost of the greater H2/(CO + CO2) ratio is higher than that from
methanol synthesis process, the operation pressure syngas with a lesser H2/(CO + CO2) ratio, whereas the
range should be maintained as low as possible and selectivity of methanol from syngas with a greater CO2/
should match with the upper and downstream process. CO ratio is lower than that from syngas with a lower
(3) The choice of space velocity should be determined CO2/CO ratio. At the optimum temperature range, the
by the composition of syngas, which should be operated difference in yield and selectivity between bio-syngas
at the lowest possible range. and conventional syngas can be small. The difference
(4) Methanol synthesis, combined with electricity or in yield is 27% and 5%, respectively, and the difference
heat supply, is highly recommended to improve the total in selectivity is 0.6% and 2%, respectively, for syngas 1
efficiency of the system in practical application. and syngas 2. When the CO2/CO ratio is >1, the
(5) The life of the catalyst is relevant to the operating selectivity of methanol decreases sharply. The yield of
parameter and composition of the syngas. methanol is sensitive to the H2/(CO + CO2) ratio,
In the present study, the test run is ∼100 h. Catalyst whereas the selectivity of methanol is more sensitive
deactivation was measured after 100 h, because of the to the CO2/CO ratio.
influence of water in the product. Thus, it is important
(3) Because of the specific composition of the syngas
to seek a highly stable catalyst for biomass-derived
derived from air-steam gasification, the yield of metha-
syngas application.
nol would be lower than that from catalytic gasification,
whereas the selectivity of methanol is higher for the
Conclusions
former syngas. With a partial removal of CO2, both yield
The characteristics of methanol synthesis from bio- and selectivity of methanol can be improved. The
mass-derived syngas have been investigated, and the optimum selectivity of methanol for syngas derived from
following conclusions can be drawn from the results: air-steam gasification is 98%. Optimum selectivity for
(1) Both the yield and selectivity of methanol are syngas derived from catalytic gasification is dependent
affected by the operating parameters, such as temper- on the CO2/CO ratio of the syngas, exhibiting values of
ature, pressure, and space velocity. Optimum conditions 92% and 97% for syngas 2 and syngas 4, respectively.
for the yield of methanol exist at certain temperatures It suggests that the partial removal of CO2 in the
and are favorable with higher pressure and space further process can lighten the burden of separating
velocity at the tested ranges, whereas for the selectivity water from methanol.
of methanol, the optimum conditions are heavily related
to the composition of the syngas. For a typical bio-
Acknowledgment. The authors acknowledge the
syngas derived from catalytic gasification (syngas 2), the
CRCG of the University of Hong Kong and Chinese
optimum temperature is ∼245°C; higher pressure and
Academy of Sciences for supporting this project.
lower space velocity can increase the selectivity of
methanol. EF0498622