Escolar Documentos
Profissional Documentos
Cultura Documentos
Review
India
c Homi Bhabha National Institute, Anushaktinagar, Mumbai 400094, India
a b s t r a c t
Methanol demand is continuously increasing in the chemical and energy industries. It is commercially produced from
synthesis gas (CO + CO2 + H2 ) using CuO/ZnO/Al2 O3 catalysts. Today, much effort is being put on the development of
technologies for its production from carbon dioxide (CO2 ). In this way, the Greenhouse effect may be mitigated. Over
the years, several useful works on CO2 hydrogenation to methanol have been reported in the literature. In this article,
we present a comprehensive overview of all the recent studies published during the past decade. Various aspects
on this reaction system (such as thermodynamic considerations, innovations in catalysts, inuences of reaction
variables, overall catalyst performance, reaction mechanism and kinetics, and recent technological advances) are
described in detail. The major challenges confronting methanol production from CO2 are considered. By now, such
a discussion is still missing, and we intend to close this gap in this paper.
2014 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Keywords: Methanol; Syngas; Carbon dioxide; Carbon Monoxide; Hydrogenation; Cu/ZnO Catalyst; Pd Catalyst
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2558
2. Methanol from catalytic hydrogenation of CO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2558
3. Thermodynamic analysis of catalytic CO2 hydrogenation to methanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2559
4. Discussion on catalytic features . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2559
4.1. Recent advances in Cu-based catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2560
4.2. Pd-based catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2562
4.3. Other catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2562
5. Knowledge on reaction pathway . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2562
6. Recent technological advances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2563
6.1. Current industrial status . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2563
Corresponding author. Tel.: +91 22 33612014; fax: +91 22 33611020.
E-mail addresses: pd.vaidya@ictmumbai.edu.in, pdvaidya@gmail.com (P.D. Vaidya).
Available online 15 March 2014
http://dx.doi.org/10.1016/j.cherd.2014.03.005
0263-8762/ 2014 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
2558 chemical engineering research and design 9 2 ( 2 0 1 4 ) 25572567
earlier reported by Liu et al. (2003), and thus, is excluded from higher catalytic activity than CuO/ZnO/Al2 O3 . The addi-
the scope of this work. tion of Mn to CuO/ZnO/ZrO2 , even at low concentration
Since 2003, Cu- and Pd-based catalysts have been exten- (2 wt%), resulted in increased methanol production rates. At
sively studied; these investigations are described in detail T = 220 C, P = 8 MPa, GHSV = 3400 l/h and H2 /CO2 = 3 (mol/mol),
here. Besides, few works on other promising catalysts are the methanol yield and selectivity were 138 g/(kgcat h) and
highlighted, too. 91%, respectively. Guo et al. (2011) prepared CuO/ZnO/ZrO2
catalysts via a route of solid-state reaction. They investigated
4.1. Recent advances in Cu-based catalysts the effects of calcination temperature on the physicochemi-
cal properties of the catalysts and found that Cu dispersion
Cu-based catalysts (e.g., CuO/ZrO2 , CuO/ZnO/ZrO2 , decreases with an increase in the calcination temperature.
CuO/ZnO/Ga2 O3 , modied CuO/ZnO/Al2 O3 and multi- A phase transformation of ZrO2 from tetragonal to mono-
component catalysts) have been extensively studied. clinic was observed. The highest activity was achieved using
Furthermore, many Cu-based catalysts promoted by B, V the catalyst which was calcined at 400 C. For example, at
and Ga have been investigated, too. To illustrate the potential T = 240 C, P = 3 MPa, space velocity = 3600 1/h and H2 /CO2 = 3
of catalysts containing Cu and Zr in methanol synthe- (mol/mol), the values of CO2 conversion, methanol selectivity
sis, Raudaskoski et al. (2009) reviewed recent work done and yield were 15.7, 58 and 9.1%, respectively. In another
by various researchers. Even so, we are describing these investigation, Guo et al. (2009) synthesized CuO/ZnO/ZrO2
studies in further detail. Liu et al. (2001) found that the catalysts using urea-nitrate combustion method. They stud-
catalyst composition and the catalyst preparation meth- ied the effects of the urea/nitrate ratio on catalyst properties
ods and conditions have an enormous inuence on the and performance. From their results, they concluded that
surface structure of catalysts. For example, CuO/ZrO2 cat- the investigated catalyst exhibits optimum behaviour when
alyst prepared by deposition-precipitation (DP) had ner 50% of the stoichiometric amount of urea is used. Using this
particles and higher catalytic activity than the catalysts catalyst at T = 240 C, P = 3 MPa, space velocity = 3600 1/h and
prepared by impregnation or co-precipitation. When DP H2 /CO2 = 3 (mol/mol), the values of CO2 conversion, methanol
catalyst (CuO/ZrO2 = 30/70 by wt.) calcined at 350 C was used, selectivity and yield were 17, 56.2 and 9.6%, respectively.
methanol yield of 0.36 g/(gcat h) was obtained at T = 240 C, Arena et al. (2007) used a novel synthesis route based on
P = 2 MPa, space velocity = 5400 1/h and H2 /CO2 = 3 (mol/mol). reverse co-precipitation under ultrasound irradiation to
Sloczynski et al. (2003) studied the effect of addition of Mg prepare CuO/ZnO/ZrO2 catalysts. This method provided a
and Mn promoters on the catalytic activity and adsorptive signicant improvement in the total surface exposure and the
properties of CuO/ZnO/ZrO2 . A catalyst preparation method dispersion and surface area of the active metal phase. ZnO
which required decomposition of the citrate complexes of the had a strong promoting effect on the texture of the catalyst.
metals was used. With the addition of these promoters, Cu The investigated reaction was deemed structurally sensitive,
dispersion was enhanced. The surface layers were depleted due to the fact that TOF changed appreciably with metal
of Cu and enriched in Zn and Zr. In effect, the promoters were dispersion. The activity of CuO/ZnO/ZrO2 was compared with
preferentially accumulated on the surface of the catalysts. that of the conventional methanol synthesis catalyst (viz.
A correlation between the adsorptive properties and the CuO/ZnO/Al2 O3 ) over the ranges in temperature, 160260 C,
catalytic activity was established. An overall factor combining and pressure, 13 MPa. Due to a stronger afnity to water, the
the catalytic activity and the adsorptive properties favouring performance of the Al2 O3 -based catalyst was poorer. From
methanol synthesis was considered. It was found that this a thermodynamic analysis, it was concluded that methanol
factor increases in the order CuZnZr < CuZnZrMg < CuZnZrMn. formation proceeds via CO2 hydrogenation.
Using a successive precipitation technique, Yang et al. (2006) Recent investigations using catalysts containing Cu, Zn and
prepared CuO/ZnO catalyst doped with ZrO2 . They found that Al are represented in Table 3 (An et al., 2007; Gallucci et al.,
the presence of ZrO2 led to higher copper dispersion which 2004; Hong et al., 2002; Melian-Cabrera et al., 2002a; Saito and
was distinctive from that of CuO/ZnO. The CO2 conversion Murata, 2004). Gallucci et al. (2004) used a zeolite membrane
(26.4%) and methanol yield (0.22 g/(mL h)) using ZrCuO/ZnO reactor that combined catalytic reaction over CuO/ZnO/Al2 O3
at T = 250 C, P = 5 MPa, space velocity = 4000 1/h and H2 /CO2 = 3 with separation properties of zeolite membranes. They found
(mol/mol) were considerably higher than those obtained using that the values of CO2 conversion, methanol selectivity and
CuO/ZnO (16% and 0.14 g/(mL h)). Jung and Bell (2002) studied methanol yield were higher than those obtained in a tradi-
the effect of zirconia phase and copper to zirconia surface tional reactor. Hong et al. (2002) reported high catalytic activity
on catalyst activity. The catalysts prepared using m-ZrO2 and selectivity of ultrane CuO/ZnO/Al2 O3 catalyst which
support were 4.5 times more active than those prepared using was prepared by using a novel gel-network-coprecipitation
t-ZrO2 support. Due to higher concentrations of the active method. Melian-Cabrera et al. (2002a) studied the effect of Pd
intermediates, the rate of methanol synthesis on Cu/m-ZrO2 on the performance of a CuO/ZnO/Al2 O3 catalyst. When cata-
was higher. Raudaskoski et al. (2007) studied the effect of lysts containing 4 and 10 wt% Pd were used at P = 4 MPa and
ageing time during co-precipitation. It was found that the W/F = 0.042 kg h/m3 over the temperature range 160200 C,
prolonged suspension ageing time during the preparation of values of the intrinsic methanol yield (mol methanol/h/mol
CuO/ZnO/ZrO2 is advantageous for catalytic activity. As the exposed Cu) were substantially higher than those obtained
ageing time increased, the sodium content of the catalyst using the catalyst without Pd. It was found that Pd improves
decreased and ner crystallite structures were formed. the reducibility of CuO. The intrinsic promoting effect of Pd
Besides, several other useful works using CuO/ZnO/ZrO2 was attributed to a hydrogen spill over mechanism. Saito
are reported in the literature, too. These works are and Murata (2004) found that multi-component catalysts such
summarized in Table 2 (Arena et al., 2007; Guo et al., as Cu/ZnO/ZrO2 /Al2 O3 and Cu/ZnO/ZrO2 /Al2 O3 /Ga2 O3 were
2009, 2011; Lachowska and Skrzypek, 2004). Lachowska highly active for methanol synthesis from CO2 and H2 . The
and Skrzypek (2004) found that CuO/ZnO/ZrO2 had stability of these catalysts vastly improved even when a small
chemical engineering research and design 9 2 ( 2 0 1 4 ) 25572567 2561
Table 2 Recent works on CO2 conversion into methanol using CuO/ZnO/ZrO2 catalyst.
Catalysts Preparation Salient features of work Reference
CuO/ZnO/ZrO2 Thermal decomposition of citrates CuO/ZnO/ZrO2 has higher catalytic Lachowska and Skrzypek (2004)
Mn-promoted-CuO/ZnO/ZrO2 activity than CuO/ZnO/Al2 O3 .
Addition of Mn to CuO/ZnO/ZrO2
results in increased methanol
production rates.
CuO/ZnO/ZrO2 Solid-state reaction Cu dispersion decreases with an Guo et al. (2011)
increase in the calcination
temperature.
The highest activity is achieved
using the catalyst, which is
calcined at 400 C.
CuO/ZnO/ZrO2 Urea-nitrate combustion method The catalyst exhibits optimum Guo et al. (2009)
behaviour when 50% of the
stoichiometric amount of urea is
used.
CuO/ZnO/ZrO2 Reverse co-precipitation under This method provides a signicant Arena et al. (2007)
ultrasound irradiation improvement in the total surface
exposure and the dispersion and
surface area of the active metal
phase.
CO2 conversion into methanol is
structurally sensitive.
amount of colloidal silica was added. Crude methanol pro- precipitation technique. As a result of Pd incorporation,
duced in this way in a bench-scale unit (purity 99.9%) was methanol yield was considerably higher. Using this catalyst
cleaner than that produced in a commercial syngas-based at T = 240 C, P = 6 MPa and W/F = 0.0675 kg h/m3 , it was found
methanol plant. Using co-precipitation technique, An et al. that the values of CO2 conversion and methanol selectivity
(2007) prepared a series of Cu/Zn/Al/Zr catalysts containing were 9.2 and 66.2%, respectively (Melian-Cabrera et al., 2002c).
different ratios of Al/Zr. It was found that these catalysts com- Toyir et al. (2001a) prepared CuO/ZnO/Ga2 O3 catalyst by co-
prised Cu/Zn crystallites in a brous structure. The dispersion impregnation of methoxide-acetylacetonate precursors from
and stability of the crystallites for these catalysts were supe- methanolic solutions onto ZnO support. Due to the presence of
rior to those for a commercial CuO/ZnO/Al2 O3 catalyst. As a Ga2 O3 promoter and high Cu dispersion, this catalyst had high
result, CO2 hydrogenation was enhanced. When Zr was added activity, selectivity and stability. At T = 270 C and P = 2 MPa, the
(5%), the methanol space time yield was 80% higher than that rate of methanol formation was 378 g/(kgcat h), whereas the
for a commercial catalyst. selectivity to methanol was 88%.
Few studies using other CuO/ZnO-based catalysts are Besides these works, there are some other investigations
reported in the recent literature. For example, Melian-Cabrera using -Al2 O3 supported Cu-based catalysts. Zhang et al.
et al. (2002b) compared the efcacy of CuO/ZnO with Pd- (2006) investigated the effect of addition of Zr to a CuO/-Al2 O3
promoted CuO/ZnO catalyst prepared by using sequential catalyst using impregnation technique. Due to the enhanced
dispersion of CuO, both the catalytic activity and selectiv- Ga2 O3 -promoted Pd/SiO2 at T = 250 C and P = 3 MPa were
ity towards methanol improved after Zr addition. In another 0.0017 and 0.45 1/s, respectively. The initial methanol selec-
work (Zhang et al., 2007), the effect of addition of V was tivity at these conditions was 17 and 62%, respectively. This
studied, too; the efcacy of CuV/-Al2 O3 was higher than unusually high catalytic behaviour was attributed to the inter-
that of Cu/-Al2 O3 . The inuence of reaction variables on the action of Pd crystallites with reduced Ga species. According to
performance of 12%Cu6%V/-Al2 O3 was studied, and it was Collins et al. (2002, 2005), the successful promotion of Pd/SiO2
found that the most favourable conditions for methanol for- by Ga is due to the closeness of the Ga2 O3 Pd functions and
mation are T = 240 C, space velocity = 3600 1/h and H2 /CO2 hydrogen spill over onto the SiO2 support.
ratio = 3 mol/mol. Wang et al. (2002) found that the perfor- Thus, the performance of Pd as a catalyst for CO2 conver-
mance of CuO/CeO2 /-Al2 O3 and CuO/YDC/-Al2 O3 (where sion to methanol appears promising. In our opinion, much
YDC denotes yttria-doped ceria) is superior than that of effort should be focused on Pd-based catalysts in future.
CuO/-Al2 O3 . They attributed this enhanced efcacy to the
synergistic effect between CuO and surface oxygen vacancies
4.3. Other catalysts
of CeO2 .
Interestingly, catalysts containing Cu and Ga are reported
Transitional metal carbides, which are metal-derived com-
in the literature, too. For instance, Toyir et al. (2001b) found
pounds comprising carbon in the metal lattice, are potentially
that CuO/Ga2 O3 /SiO2 catalysts prepared by impregnation
attractive catalysts for CO2 hydrogenation (Ma et al., 2009).
method were highly selective and stable in the temperature
They are characterized by high melting point and hardness,
range, 250270 C. The use of hydrophobic SiO2 enhanced the
and have good thermal and mechanical stability. Their ef-
activity, selectivity and stability of the catalyst. The modi-
cacy for hydrogenation reactions is comparable to those of
cation of properties of Cu particles was attributed to the
noble metals such as Pt and Rh (Levy and Boudart, 1973;
presence of very small particles of Ga2 O3 on the surface.
Oyama, 1992). Besides, their hydrogen adsorption, activation
Liu et al. (2005) used nano-crystalline ZrO2 as support for
and transfer capabilities are superior to those of metal sulp-
the preparation of CuO/Ga2 O3 /ZrO2 and CuO/B2 O3 /ZrO2 cata-
hides. Dubois et al. (1992) investigated CO2 hydrogenation
lysts. At T = 250 C, P = 2 MPa and space velocity = 2500 1/h, the
using transition metal carbides. Mo2 C and Fe3 C showed high
values of methanol yield for the Ga- and B-containing cata-
CO2 conversion and methanol selectivity at T = 220 C. Cu
lysts were 1.93 and 1.8 mmol/(g h), respectively. It was found
addition to Mo2 C lowered the hydrocarbon selectivity. A con-
that nano-crystalline ZrO2 changes the electronic structure
siderable amount of dimethyl ether was produced over WC.
and affects the metal and support interactions on the cata-
It was found that TaC and SiC were almost inactive. It is thus
lyst. Consequently, this results in facile reduction, intimate
obvious that much effort should be focused for further improv-
interaction between Cu and ZrO2 , more corner defects and
ing their performance.
oxygen vacancies on the surface of the catalyst. The values
The AB1x Bx O3 perovskite catalyst, which contains mixed
of CO2 conversion and methanol selectivity were higher than
valence ions and catalytic active sites, has high activity for CO2
those obtained using catalysts prepared by conventional co-
conversion to methanol. For example, Jia et al. (2009) reported
precipitation technique.
that the catalytic activity (XCO2 = 10.4% and SMeOH = 90.8%) of
From all the above-mentioned studies, it may be noted that
a pre-reduced lanthanum chromite perovskite catalyst doped
Cu-based catalysts are promising for methanol production via
with Cu (viz. LaCr0.5 Cu0.5 O3 ) was superior to that of 13%
CO2 hydrogenation.
Cu/LaCrO3 catalyst (XCO2 = 4.8% and SMeOH = 46.6%) at 250 C.
The catalytic activity was higher, due to the fact that H2 was
4.2. Pd-based catalysts
adsorbed on the Cu+ sites and CO2 was activated on the
medium basic sites.
Pd has high efcacy for CO2 hydrogenation to methanol (Ma
Clearly, novel catalysts described in this section are effec-
et al., 2009); however, the activity and selectivity of Pd-based
tive; even so, further investigations are essential before one
catalysts depend on the type of support (Shen et al., 2001), and
can deduce the practical feasibility of such catalysts.
the method of catalyst preparation (Kim et al., 2003). Several
studies using Pd have recently been published.
Liang et al. (2009) developed Pd/ZnO catalysts supported 5. Knowledge on reaction pathway
on multi-walled carbon nanotubes (MWCNTs), which showed
excellent performance for CO2 hydrogenation to methanol. At There are few previous works describing the reaction pathway
P = 3 MPa and T = 250 C, the observed TOF for CO2 hydrogena- of methanol from syngas using Cu/ZnO catalyst (Chinchen
tion reached 1.15 102 1/s using 16% Pd0.1Zn1/CNTs (h-type). et al., 1986, 1987; Edwards and Schrader, 1984; Klier et al., 1982;
Using Pd/ZnO at 0.1 MPa pressure, Iwasa et al. (2004) reported Lim et al., 2009; Sahibzada, 2000). Klier et al. (1982) reported
higher TOF and methanol selectivity than Cu/ZnO. PdZn alloys that methanol production was promoted even at low CO2
were formed by catalyst reduction at high temperature. These concentration in CO/CO2 /H2 mixtures, although the synthe-
alloys served as active sites for methanol synthesis. sis was inhibited in CO2 -rich atmospheres. A CO2 /CO redox
Collins et al. (2004) investigated the interaction of CO2 mechanism was employed to describe the kinetic promo-
and H2 /CO2 with pure -Ga2 O3 and Pd/-Ga2 O3 . They pro- tion/inhibition with respect to the CO2 /CO fraction (Chinchen
posed that the addition of Pd to the oxide support increases et al., 1986; Klier et al., 1982). According to this mecha-
the hydrogenation rate of all the carbon-containing species nism, Cu is reduced or oxidized by the adsorption of CO and
bonded to the -Ga2 O3 surface by spill over of atomic hydrogen CO2 , respectively (Klier et al., 1982). Interestingly, Chinchen
from metallic Pd to Ga2 O3 . et al. (1987) investigated methanol synthesis from CO/CO2 /H2
Bonivardi et al. (2000) found that the addition of using isotope-labelled 14 CO2 and established that most of the
Ga to Pd/SiO2 resulted in enhanced catalytic perfor- methanol was produced from CO2 . Then, Sahibzada (2000)
mance. For example, the values of TOF using Pd/SiO2 and found that CO2 did not inhibit methanol synthesis. Rather,
chemical engineering research and design 9 2 ( 2 0 1 4 ) 25572567 2563
the progressive inhibition in CO2 -rich atmosphere was due the H2 COOH intermediate, and further hydrogenation of H2 CO
to the increasing product water concentration as a result to H3 CO and H3 COH. They concluded that methanol synthe-
of Eq. (3) (CO2 + 3H2 CH3 OH + H2 O) and the reverse of Eq. sis from direct hydrogenation of the formate on Cu(1 1 1) is
(4) (H2 + CO2 CO + H2 O). The activity of Cu/ZnO catalyst not feasible due to the high activation barriers for some of the
for methanol synthesis from CO2 /H2 was improved by the elementary steps. Contrarily, it was suggested that the CO2
addition of Pd, due to the fact that H2 spill-over from Pd hydrogenation route to hydrocarboxyl (trans-COOH) is kineti-
counteracted the inhibition by water. At low water concentra- cally more favourable than formate in the presence of H2 O via
tion, it is possible that, in a CO-rich atmosphere, methanol is a unique hydrogen transfer mechanism. First, the trans-COOH
produced by CO hydrogenation in addition to CO2 hydrogena- is converted into hydroxymethylidyne (COH) via dihydrox-
tion using Cu/ZnO (Sahibzada, 2000). Edwards and Schrader ycarbene (COHOH) intermediates. Next, three consecutive
(1984) showed that CO is adsorbed in the form of a carbonyl hydrogenation steps occur, thereby resulting in the formation
species, and the formate species is a usual intermediate for of hydroxymethylene (HCOH), hydroxymethyl (H2 COH), and
methanol synthesis and WGS reaction. Recently, Lim et al. methanol (see Table 4).
(2009) developed a kinetic model for methanol synthesis using Chiavassa et al. (2009) modelled methanol synthesis from
Cu/ZnO/Al2 O3 /ZrO2 catalyst. They considered that CO and CO2 CO2 /H2 over Ga2 O3 Pd/SiO2 catalyst, along with the reverse
are adsorbed on different sites on Cu (here denoted as s1 WGS reaction. They found that hydrogenation of the formate
and s3 ). From their results, they concluded that the surface intermediate and its decomposition on the Ga2 O3 surface were
reaction of a methoxy species, the hydrogenation of a for- the rate determining steps, respectively. From their results,
mate intermediate (HCOO), and the formation of a formate they concluded that a competitive adsorption mechanism,
intermediate are the rate-determining steps for CO and CO2 where adsorbed atomic hydrogen occupies the same active
hydrogenation and the WGS reaction, respectively; these steps sites as other oxygenated surface intermediates on Ga2 O3 , is
are represented as: most appropriate.
Clearly, there is scarce information in the literature and
H3 CO s1 + H s2 CH3 OH + s1 + s2 (6) additional work on the reaction pathway and kinetics of CO2
hydrogenation to methanol is essential for a comprehensive
HCO2 s3 + H s2 H2 COO s3 + s2 (7) insight into methanol synthesis chemistry.
Table 4 Elementary reaction steps in various methanol synthesis routes from CO2 according to Zhao et al. (2011).
Reaction routes Reactions
H2 H + H
CO2 + H mono-HCOO bi-HCOO
mono-HCOO CO + OH and bi-HCOO HCO + O
bi-HCOO + H H2 COO and bi-HCOO + H HCOOH
Formate reaction route H2 COO + H H2 COOH and HCOOH + H H2 COOH
HCO + H H2 CO and H2 COO H2 CO + O and
H2 COOH H2 CO + OH
H2 CO + H H3 CO
H3 CO + H H3 COH
H2 H + H
CO2 + H trans-COOH
trans-COOH cis-COOH
trans-COOH + H t,t-COHOH t,c-COHOH c,c-COHOH
Hydrocarboxyl reaction route c,c-COHOH COH + OH and t,c-COHOH COH + OH
COH CO + H and HCO CO + H and cis-COOH CO + OH
COH + H HCOH and HCO + H HCOH
HCOH + H H2 COH and H2 CO + H H2 COH
H2 COH + H H3 COH
from methanol synthesis) or a single step approach proposed temperature and at high yield. In the second bed, the reac-
by NIRE/RITE (the two stages integrated in a single reactor) tion heat was used to pre-heat the feed gas to the rst bed.
(Centi et al., 2008). The rst approach seems preferable in The continuously reduced temperature in this bed provided
terms of higher catalyst productivity, lower gas recycle and increasing thermodynamic equilibrium potential. In this bed,
reactor size (Centi and Perathoner, 2009). the reaction rate was much lower, and hence, was the reac-
Very recently, researchers at the Institute of Bioengineering tion heat. This feature resulted in milder temperature proles
and Nanotechnology (IBN) in Singapore used organocatalysts in the second bed because less heat was released as com-
to activate CO2 in a mild and non-toxic process for producing pared to the rst bed. In this way, the catalysts were exposed
methanol. Certainly, all these developments are very encour- to less extreme temperatures and, catalyst deactivation via
aging. sintering was avoided. The two-stage catalyst bed system
could be operated with higher conversion and longer cata-
lyst life time than a conventional single-bed reactor. Thus,
6.2. Reactor innovations
it is an interesting candidate for application in methanol
production.
There are few recent works which consider innovations in
reactors; these are briey discussed in this subsection. To
combine catalytic reaction with the separation properties of
zeolite membranes, Gallucci et al. (2004) used a zeolite mem- 6.3. Alternate catalytic CO2 hydrogenation techniques
brane reactor. They found that CO2 conversion (XCO2 = 11.6%), for methanol synthesis
methanol selectivity (SMeOH = 75%) and yield (YMeOH = 8.7%)
at T = 206 C were higher than those obtained in a con- Joo et al. (1999) reported CAMERE (CO2 hydrogenation to form
ventional reactor (XCO2 = 5%, SMeOH = 48% and YMeOH = 2.4%) methanol via a reverse WGS reaction) process to convert CO2
at T = 210 C, P = 2 MPa, H2 /CO2 ratio = 3 mol/mol and space into methanol. This process comprised a reverse WGS reaction
velocity = 6000 1/h. The methanol yield was higher, due to and a methanol synthesis reaction. CO2 and H2 were converted
the fact that the products (methanol and water) were to CO and H2 O by the reverse WGS, and then the gaseous mix-
selectively removed from the reaction system. From reac- ture of CO/CO2 /H2 was fed into the methanol reactor after
tor simulations at T = 210 C and P = 1 MPa, Barbieri et al. removing water. Several useful papers on the CAMERE pro-
(2002) found that reactors with an organophilic (X = 22.7%, cess were published during the past decade (Park et al., 2000,
SMeOH = 60.2%, YMeOH = 13.7%) and hydrophilic membrane 2001; Joo and Jung, 2003).
(X = 23.9%, SMeOH = 54.2%, YMeOH = 13%) have better perfor- Low temperature methanol synthesis in a liquid medium
mance than that of a conventional tubular reactor (X = 14.2%, is a candidate technique reported in the literature. Accord-
SMeOH = 40.5%, YMeOH = 5.8%). They highlighted the fact that ing to Xu et al. (2009), this technology is expected to produce
increased methanol yield in a membrane reactor reduces the methanol more efciently than the conventional methanol
consumption of reactant and facilitates operation at lower production processes using Cu/ZnO-based catalysts, due to
pressures and higher temperatures. This, in turn, favours reac- the fact that it has several advantages over the conventional
tion kinetics by reduction in the residence time and the reactor process, i.e., thermodynamically favourable low temperature
volume. operation and efcient removal of the heat of reaction due to
Rahimpour (2008) investigated a two-stage catalyst bed the large heat capacity of a liquid medium. Recently, Liu et al.
concept for CO2 conversion to methanol. A system with two (2007) employed a novel low-temperature route in an auto-
catalyst beds instead of one single catalyst bed was consid- clave for the efcient conversion of CO2 into methanol. Using
ered. In the rst catalyst bed, the synthesis gas was partly this process, 25.9% CO2 conversion and 72.9% methanol selec-
converted to methanol in a conventional water-cooled reac- tivity was achieved at a low temperature of 443 K and pressure
tor. This bed was operated at higher than normal operating of 5 MPa using alcohol as solvent.
chemical engineering research and design 9 2 ( 2 0 1 4 ) 25572567 2565
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