A Novel Consecutive Approach for the Preparation of Cu–MgO Catalysts with High Activity for Hydrogenation of Furfural to Furfuryl Alcohol

Article abstract of DOI:10.1007/s10562-016-1948-6

Abstract: A consecutive approach is introduced and tested for the first time to synthesize copper-magnesia catalysts with different (Cr, Ca, and Co) promoters for the catalytic hydrogenation of furfural. The comparison of the activity of these catalysts with that prepared via conventional co-precipitation indicated the superior activity of the former. A stable conversion of furfural (up to 91%) to furfuryl alcohol was achieved over the thus-prepared Cu–MgO and CaCu–MgO catalysts. However, both CoCu–MgO and CaCu–MgO demonstrated higher selectivities (about 99%) than the other two samples (Cu–MgO and CrCu–MgO). No direct interconnection was established between the catalytic activity and structural features of the catalysts, however. Graphical Abstract: [Figure not available: see fulltext.]

Full text of DOI:10.1007/s10562-016-1948-6

Catal Lett
DOI 10.1007/s10562-016-1948-6
A Novel Consecutive Approach for the Preparation of Cu–MgO
Catalysts with High Activity for Hydrogenation of Furfural
to Furfuryl Alcohol
1
Mohammad Ghashghaee · Samahe Sadjadi · Samira Shirvani
,2
2,3
1,2
·
1
,2
Vahid Farzaneh
Received: 17 September 2016 / Accepted: 6 December 2016
Springer Science+Business Media New York 2017
©
Abstract A consecutive approach is introduced and
tested for the first time to synthesize copper-magnesia
catalysts with different (Cr, Ca, and Co) promoters for the
catalytic hydrogenation of furfural. The comparison of the
activity of these catalysts with that prepared via conven-
tional co-precipitation indicated the superior activity of the
former. A stable conversion of furfural (up to 91%) to fur-
furyl alcohol was achieved over the thus-prepared Cu–MgO
and CaCu–MgO catalysts. However, both CoCu–MgO and
CaCu–MgO demonstrated higher selectivities (about 99%)
than the other two samples (Cu–MgO and CrCu–MgO). No
direct interconnection was established between the catalytic
activity and structural features of the catalysts, however.
Graphical Abstract
Keywords Hydrogenation · Furfuryl alcohol · Furfural ·
Copper catalysts · Hydrothermal synthesis.
1
Introduction
Energy security issues, environmental concerns such as
the increase in the green house gases and consequently
global warming [1] together with the depletion of the crude
reserves [2–4] have led to increasing the use of low-carbon
biofuels derived from lignocellulosic or oleochemical bio-
mass sources as alternatives to fossil fuels [5–10].
*
Mohammad Ghashghaee
m.ghashghaee@ippi.ac.ir
Furfural is among the most promising biomass-derived
molecules, which can be potentially used for the synthesis
of a broad range of value-added chemicals such as furoic
acid, 2-methylfuran, furfurylamine, maleic acid, furan,
linear alkanes, 1,5-pentanediol, cyclopentanone, 2-methyl
tetrahydrofuran, furfuryl alcohol and fuels [8, 11–18].
Among the chemical transformations of furfural, catalytic
hydrogenation of furfural which can be achieved in liquid
1
2
Faculty of Petrochemicals, Iran Polymer and Petrochemical
Institute, P.O. Box 14975-112, Tehran, Iran
Biomass Conversion Science and Technology (BCST)
Division, Iran Polymer and Petrochemical Institute, P.O.
Box 14975-115, Tehran, Iran
3
Gas Conversion Department, Faculty of Petrochemicals, Iran
Polymer and Petrochemical Institute, P.O. Box 14975-112,
Tehran, Iran
[13, 19–21] or gas [10, 22, 23] phases in the presence of
Vol.:(0123456789)
1 3

M. Ghashghaee et al.
metal-based catalysts is of particular importance [8]. The
utility of furfuryl alcohol for the production of adhesives,
furan fiber-reinforced plastics, thermostatic resins, liquid
resins, foundry resins, farm chemicals, lubricants, dispers-
ing agents, ascorbic acid, and lysine has been proven [22,
the purchase. Mg(NO ) ·6H O (ACS reagent, 99%),
3
2
2
Cu(NO ) ·3H O (99.5%), K CO (ACS reagent, 99.5%),
3
2
2
2
3
Ca(NO ) ·4H O (99%) and Co(NO ) ·6H O (99%) were
3 2
3
2
2
2
provided from Merck. Cr(NO ) ·9H O (97%) was pur-
3
3
2
chased from Scharlau. The material employed for the study-
ing the catalytic activity included furfural (98.90%, Merck)
and high purity hydrogen (99.99%) and nitrogen (99.99%).
2
4–26].
Industrially, the gas-phase hydrogenation of furfural is
accomplished at temperatures ranging between 403 and
73 K and pressures up to 30 bar under commercial cop-
4
2.2 Catalyst Preparation Using Co-Precipitation
Method
per chromate catalysts [9, 27]. Copper chromate can result
in selective formation of furfuryl alcohol. However, this
catalyst is toxic and exhibited moderate activity. To fur-
nish a solution to these problems many attempts have been
devoted to develop alternative Cr-free catalysts. To date,
various mono metallic and bimetallic catalysts including
Cu, Ni, Pd, Co, Ru, Ir, and Pt supported on a relatively inert
material such as silica and alumina have been prepared [16,
A catalyst sample, which is referred to as CM0, was pre-
pared by conventional co-precipitation method. Briefly,
1 M solution of K CO was added to a mixture of
2
3
Cu(NO ) ·3H O (1 M) and Mg(NO ) ·6H O drop wisely to
3 2
3
2
2
2
form precipitate at a pH of 9.0. The resulting solution was
stirred vigorously for 3 h. Upon completion, the precipitate
was filtered and washed with distilled water and dried at
393 K for 15 h. The final catalyst was obtained by calcina-
tion in air at 723 K for 5 h with the heating rate of 1 K/min.
2
8–32] among which Cu-based catalysts, especially Cu-
MgO has gained increasing attention because of its low
cost, high activity and selectivity to furfuryl alcohol [17,
2
2, 28, 33–36].
Herein, we wish to present a novel procedure based on a
2.3 Catalyst Preparation Using Consecutive Approach
combination of co-precipitation and hydrothermal methods
for the preparation of a series of Cu–MgO catalysts with
various promoters (Co, Ca, and Cr) and definite morpholo-
gies. The main reason for using the promoters and develop-
ing the multimetallic catalysts was taking advantages of the
multicomponent catalyst systems compared to monometal-
lic counterparts and consequently improving the catalytic
performance of the catalyst. Cr is a promoter widely used
for improving the catalytic performance of the Cu–MgO
catalysts [37–39]. It is even used in the commercialized
catalyst used for industrial conversion of furfural to furfu-
ryl alcohol. Ca is a basic promoter which in proper amount
can improve the stability of the Cu-based hydrogenation
catalysts [40]. According to previous reports, Co promoter
can increase the selectivity of the process by reducing the
unwanted by-products [41]. Therefore, these three promot-
ers were chosen for possible effects on the base catalyst.
The catalytic activities of these catalysts as well as the
effects of the promoters on the catalytic performances are
studied for the gas-phase hydrogenation of furfural to fur-
furyl alcohol. Moreover, the catalytic activities of Cu-MgO
catalysts prepared via the new consecutive approach and
the classic co-precipitation method are compared.
The catalysts were prepared by a novel consecutive proce-
dure based on a combination of co-precipitation and hydro-
thermal methods. The typical procedure includes precipita-
tion of a mixture of 1 M solution of Cu(NO ) ·3H O and
3
2
2
Mg(NO ) ·6H O with the percentage weight ratio of 16:84
2
3
2
for Cu:MgO by drop wise addition of 1 M aqueous solution
of K CO at room temperature at a pH of 9.0 followed by
2
3
stirring for 3 h. Subsequently, the mixture was transferred
to a Teflon-lined autoclave and subjected to hydrothermal
treatment for 24 h at 200°C. The precipitate was filtered
and washed with distilled water. The final catalyst, named
as CM1, was obtained by drying the precipitate at 423 K
for 15 h and calcination in air at 723 K for 5 h with the
heating rate of 1 K/min. Three other catalysts were also
prepared according to the above-mentioned procedure for
CM1 except that three different promoters (P) including
Cr(NO ) ·9H O, Ca(NO ) ·4H O and Co(NO ) ·6H O with
3
3
2
3 2
2
3 2
2
percentage weight ratio of 1:15:84 for P:Cu:MgO were
used. The catalysts were denoted as CM2, CM3 and CM4,
respectively.
2.4 Catalyst and Products Characterization
To characterize the novel catalysts, BET, SEM/EDX, and
XRD techniques were used along with TGA of the spent
catalysts. BET analyses were carried out via nitrogen phy-
sisorption using a Quantachrome Chembet 3000 sorp-
tion analyzer at 77 K. Prior to analysis, the samples were
degassed at 393 K for 3 h. SEM/EDX analyses of all
catalysts were performed by a Tescan instrument, using
2
Experimental
2
.1 Materials
All chemicals applied for the catalysts preparation were
used directly without any further purification after
1
3

A Novel Consecutive Approach for the Preparation of Cu–MgO Catalysts with High Activity for…
Au-coated samples with an acceleration voltage of 20 kV.
Room temperature powder X-ray diffraction patterns were
collected using a Siemens, D5000. Cobalt Co Kα radiation
was used from a sealed tube. Data were collected in the 2θ
range of 25–80° with a step size of 0.02° and an exposure
time of 2 s per step. The TGA spectra were obtained using
a Perkin Elmer Pyris 1 apparatus with 10°C/min ramping
in air. The product samples were collected in an ice-bath
condenser and taken every few minutes for analysis on a
gas chromatograph (GC) equipped with a capillary column
and a flame ionization detector (FID). The standard des-
ignation of the peaks was made by calibration on an Agi-
lent 6890 series GC system equipped with an Agilent 5973
network mass selective detector (MSD). The instrument
contained an HP-5ms column of 30 m×0.25 mm ID and
Fig. 1 The performance measures of the Cu–MgO catalysts prepared
through conventional co-precipitation and the new combined method
for the conversion of FF to FFA at 453 K, 1 atm, WHSV of 1.7 1/h,
and H /FF of 10 (Symbols X, S, and Y represent conversion, selec-
2
0
.25 µm film thickness.
tivity and yield and the numbers 1 and 2 show the results after 60
and 600 min of operation, respectively). The data were reproducible
to within ±2%
2
.5 Catalyst Activity
The catalytic activity of the catalysts for the hydrogenation
of furfural (FF) was evaluated in a tubular reactor of 10 mm
internal diameter. The catalyst (0.7 g) was initially reduced
in hydrogen flow diluted in nitrogen with the total flow rate
of ~6 l/(g h) at 523 K for 3 h and then was cooled down to
the reaction temperature of 453 K in pure hydrogen flow.
After that, the feedstock was injected into the reactor with
a space velocity (WHSV) of 1.7 g/(g h). The reactions were
experiments at different times on stream. Overall, the
feed conversion ranged from ~16 to ~91% over the whole
period of operation (~600 min) while the main prod-
uct (FFA) selectivity remained above 87% at most of the
times for all of the catalysts (Fig. 2). The conversion level
and correspondingly the yield of FFA followed the order
of CM2<CM4<CM3<CM1 as averaged over the whole
range of time-on-stream. The initial selectivity to FFA
changed in the order of CM3<CM2<CM1<CM4 while
the sequence slightly shifted to CM2<CM1<CM4<CM3
at the final times. As indicated from Fig. 2, both the par-
ent (CM1) and the calcium-doped (CM3) catalysts demon-
strated better durabilities compared to the Cr-doped (CM2)
and Co-promoted (CM4) samples (Fig. 2). Moreover, the
parent Cu-MgO catalyst (CM1) demonstrated a mild evo-
lution in its selectivity to FFA with time, whereas the rest
of the catalysts (CM2–CM4) showed an almost sustained
selectivity over an about 9 h of operation and the selectivity
of CM4 demonstrated no abrupt increase from the begin-
ning. While the FFA yield of CM3 passed through a pri-
mary maximum of ~85%, the other samples gave descend-
ing trends for the yield of FFA with time.
implemented under atmospheric conditions with an H /FF
2
volumetric ratio of 10 for 4 h. The reaction products were
analyzed by GC-MS which was equipped with an FID and
a capillary column.
3
Result and Discussion
To figure out the influence of hydrothermal treatment, the
copper-magnesia catalysts synthesized via the conventional
co-precipitation (CM0) and the new consecutive method
(
CM1) were evaluated for the selective hydrogenation of
FF to furfuryl alcohol (FFA), the key green building block
for the furan resins. Figure 1 illustrates the activity results
of the two catalysts at two times-on-stream of 60 and
When the productivity of the catalyst is concerned, the
original Cu–MgO catalyst (CM1) and the Ca-promoted
sample (CM3) were superior in terms of a relatively stable
conversion of furfural to furfuryl alcohol such that CM1
produced more FFA than CM3. On the other hand, the
CoCu–MgO catalyst (CM4) and the CaCu–MgO sample
(CM3) could be chosen if selectivity to FFA mattered most.
Among the four catalysts, the CrCu–MgO sample might be
regarded as the poorest.
6
00 min. As evident, the Cu-MgO catalyst prepared via the
new procedure (CM1) was markedly superior compared to
the conventionally synthesized sample (CM0). Although
the FFA selectivity with CM0 was striving at the initial
time of operation, it reduced drastically over the run length
and the FFA yield was too small due to the low conversion
levels compared to CM1.
Further, catalytic experiments were also conducted
to probe the additional role of Cr, Ca, and Co modifi-
ers on the performance of the mother catalyst. Figure 2
depicts the key performance data from the hydrogenation
Figure 3 depicts the averaged selectivities of the major
byproducts obtained during the reactions on the four
catalysts investigated. As indicated from this chart, the
1
3

M. Ghashghaee et al.
main reaction pathways that reduce the FFA selectivity
of CM1 were those leading to tetrahydrofurfuryl alcohol
(THFA), difurfuryl ether (FFE), 5-methylfurfural (MFF),
and 2-methylfuran (MF) while the main byproducts
over CM2 were 2-acetylfuran (AF) and MFF. The pre-
dominant byproducts over CM3 were, respectively, MFF,
THFA, 5-methylfurfuryl alcohol (MFFA), γ-valerolactone
(GVL), and AF and CM4 produced MFF and AF as the
main by-products. As such, the major byproducts over the
CrCu–MgO and CoCu–MgO catalysts were similar. This
suggests possibly that the reaction pathways over these
two catalysts have been more or less the same. The produc-
tion of THFA by Cu–MgO and CaCu–MgO samples can
also point to some common routes in the reaction networks
over these catalysts. Other significant byproducts included
2
2
-methyltetrahydrofuran (MTHF), 1-pentanol (1POL),
-pentanol (2POL), and δ-valerolactone (DVL) as is shown
in Fig. 3.
As discussed above, the use of different promoters could
clearly affect the catalytic behavior in terms of selectiv-
ity, conversion and durability. To rationalize the results,
all synthesized catalysts were characterized and compared
by using SEM/EDX, XRD, BET and elemental mapping
techniques. The measurement of BET surface areas of all
catalysts (Table 1) as well as the catalyst prepared using
co-precipitation method, CM0, demonstrated that among
the catalyst prepared by the novel procedure, even low
amounts of promoters could significantly alter the surface
area. The sample with no promoter, CM1, possessed the
2
lowest surface area, 52 m /g, while the application of Cr as
a promoter (CM2) led to the catalyst with the highest sur-
2
face area, 132 m /g. Considering the fact that CM2 exhib-
ited the poorest catalytic activity, selectivity and durability
while CM1 was the catalyst of choice, it can be concluded
that possessing a high BET surface area is not determining
for a high catalytic activity. Comparing the catalyst samples
of CM1 and CM0 which were prepared through two dif-
ferent methods established that the co-precipitation method
led to higher surface area (almost twofold) while hydrother-
mal treatment reduced remarkably the surface area.
The SEM/EDX and elemental mapping analyses of
all catalysts are depicted in Fig. 4. The cubic morphol-
ogy together with small aggregates can be detected for all
catalysts which is clearly distinguished from the aggregate
like morphology observed for CM0 sample. However, the
SEM images of the samples differ to some extent in terms
of the size of cubes, degree of aggregation and packing. In
CM1, the close-packed cubes formed compact structure.
This observation can justify the low surface area of CM1.
In the catalysts containing promoters, the size of cubes are
larger and the formation of small aggregates is more obvi-
ous. Furthermore, the degree of packing is lower than that
of CM1. Among the three catalysts, CM3 which possessed
Fig. 2 The conversion, selectivity, and yield of the synthesized cop-
per catalysts with time-on-stream in hydrogenation of FF to FFA at
453 K, 1 atm, WHSV of 1.7 1/h, and H /FF of 10. The data were
2
reproducible to within ±2%
1
3

A Novel Consecutive Approach for the Preparation of Cu–MgO Catalysts with High Activity for…
Fig. 3 Average selectivities of
byproducts obtained on the four
copper-based catalysts over a
600-min period under the reac-
tion conditions of 453 K, 1 atm,
WHSV of 1.7 1/h, and H /FF
2
of 10
Table 1 Textural properties of the Cu-MgO catalysts
The crystallite sizes of CuO were also calculated for all
catalysts (Table 2). This value changed in the order of
CM0<CM3<CM4<CM1≈CM2. Interestingly, the crys-
tallite sizes of CM1 and CM2, which exhibited the best and
the poorest catalytic performance respectively were almost
similar. Furthermore, the CM0 sample had the smallest
crystallite size. This observation indicated that hydrother-
mal treatment resulted in increase in the crystallite size.
Moreover, no clear connection between the crystallite size
as well as catalyst surface area and catalytic activity was
observed.
Sample
CuO crystallite size (nm)
Surface
area
2
m /g)
(
CM0
CM1
CM2
CM3
CM4
6.2
23.5
23.7
19.2
22.5
102
52
132
86
125
Comparing the catalytic activities of CM0 and CM1
demonstrates that the catalytic activity of CM1, which pos-
sesses a lower surface area (almost half the surface area of
CM0) and a larger crystallite size (see Table 1), surpassed
the activity of CM0. This is against the classic trends usu-
ally reported for the activity–surface area relationships.
Analogous observations have been reported limitedly in
the literature [44]. Therefore, this study clearly established
that by changing the synthetic procedure and altering the
morphology of the catalysts, the catalytic activity can be
tuned. It is suggested that the cubic morphology of the
catalyst obtained from the consecutive procedure could
provide some specific or more available active sites for the
hydrogenation reaction and prevent from the aggregation
of the reduced form of the copper species thus improving
the activity of the catalyst compared to the sample prepared
from the conventional co-precipitation method.
the second-lowest BET surface area, has the most compact
structures.
The EDX analyses (Fig. 5) of the catalysts can confirm
the formation of (P)Cu–MgO catalysts. The elemental
mapping analyses of samples proved different distributions
of catalytic species in the samples. In the cases of CM1,
CM2, and CM3, the copper species were well-distributed
over the surface of the catalyst. In CM4 sample, however,
aggregation of both copper and magnesium species are
observed. The low conversion and yield of CM4 can be
attributed to the poor distribution of these catalytic species.
According to previous reports, the low activity of CM4 can
also be attributed to the role of chromium in hampering the
reduction of copper oxide species [42]. The elemental map-
ping analyses of catalysts with promoters, CM2, CM3, and
CM4 indicated the uniform distribution of promoter on the
surface.
The TGA and DTG curves of the spent catalysts in the
temperature range of 25–800°C are depicted in Fig. 6. The
weight loss between 200 and 800°C was attributed to the
coke formed during the hydrogenation of furfural. All of
the catalysts mainly showed endotherms in the relatively
moderate temperature range of 200–460°C which can be
attributed to the soft coke [45]. As evident, the spent CM2
sample demonstrated the hardest and highest carbonaceous
deposits. On the other hand, the lowest oxidation peak
The XRD patterns of all catalysts (Fig. 5) showed the
characteristic peaks of MgO (JCPDS card No. 45-0946)
and CuO (JCPDS card No. 89-5898 and 45-0937), con-
firming the formation of the desired catalytic phases.
Noteworthy, the XRD patterns of the catalysts contain-
ing promoters were similar to those of CM1. According
to the previous reports, this observation can be attrib-
uted to high dispersion of promoters on the catalyst [43].
1
3

M. Ghashghaee et al.
Fig. 4 SEM/EDX and elemental mapping analyses of the five synthesized catalysts. a CM0, b CM1, c CM2, d CM3, and e CM4
1
3

A Novel Consecutive Approach for the Preparation of Cu–MgO Catalysts with High Activity for…
Fig. 4 (continued)
with the lowest amount of coke was obtained for the spent
CM3. These results are consistent with the activity trends
discussed in this paper. Noteworthy, the major weight loss
on CM1 occurred below 200°C, which corresponds to the
release of the physisorbed water molecules [22]. This indi-
cates that the spent CM1 catalyst possessed an exposed
Cu-MgO surface mostly uncovered by coke which sup-
ports the higher durability of this catalyst observed during
the activity tests. The possibility for the formation of soft
non-polycyclic species via condensation and rearrange-
ment reactions at low temperatures (below 200°C) cannot
be ruled out [45, 46], however. In spite of presenting a very
small DTG stage of mass loss at ~730°C which is attribut-
able to a really rigid form of coke, the spent CM0 catalyst
showed a relatively small amount of coke while performing
poorly for the vapor-phase hydrogenation of furfural. This
indicates that the catalyst did not possess appropriate active
Fig. 5 The XRD patterns of the five synthesized catalysts
1
3

M. Ghashghaee et al.
Fig. 6 Thermogravimetric (a) and derivative thermogravimetric (b) curves of the spent catalysts
sites from the beginning even to trigger the coking reac-
tions. This in turn emphasizes the influence of the prepara-
tion method on the appropriate activity of the synthesized
catalyst.
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