Fuel Processing Technology 144 (2016) 186190

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Fuel Processing Technology

journal homepage: www.elsevier.com/locate/fuproc

Higher alcohols synthesis via CO hydrogenation on Cu/Zn/Al/Zr catalysts

without alkalis and FT elements
Yong-Jun Liu, Zhi-Jun Zuo, Chao-Bo Liu, Chao Li, Xuan Deng, Wei Huang
Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China

a r t i c l e

i n f o

Article history:
Received 15 March 2015
Received in revised form 28 November 2015
Accepted 7 January 2016
Available online 14 January 2016
Keywords:
Higher alcohols
Cu/Zn/Al/Zr catalyst
CO hydrogenation
Complete liquid-phase technology

a b s t r a c t
A series of Cu/Zn/Al/Zr catalysts without alkalis and FT elements, were prepared with various atomic ratios
of Al/Zr by complete liquid-phase technology and tested for higher alcohols synthesis from CO hydrogenation.
The results showed that the Cu/Zn/Al catalyst exhibited excellent higher alcohols selectivity, reaching approximately 58.8%. With the increase of Zr/Al atomic ratio, the catalytic activity and stability increased, but methanol
became the dominant product in the liquid products over Cu/Zn/Zr catalyst. It was concluded that Al favored the
formation of higher alcohols and Zr was benecial to improve the stability of catalysts. Characterization results
showed that the addition of Zr improved the dispersion of Cu and made the catalyst easier to be reduced. It
also favored the stability of pore structure and decreased the amount of weak acidic sites. It was also found
that the amount of the weak acidic sites played a key role in the higher alcohols formation and the amount of
weak acidic sites decrease might lead to the deactivation of catalysts.
2016 Elsevier B.V. All rights reserved.

1. Introduction
Higher alcohols synthesis from syngas produced by coal or renewable biomasses has attracted researchers' interest due to their
nontoxicity and high chemical energy corresponding to that of gasoline
[1]. Currently, there are four types of catalysts for higher alcohols synthesis from CO hydrogenation: Rh-based catalysts [24], modied
methanol synthesis catalysts [57], modied FischerTropsch (FT)
synthesis catalysts [810], Mo-based catalysts [1113]. Of all these
types, only Rh-based catalysts show relatively high selectivity for the
synthesis of C2+ oxygenates due to their unique CO adsorption behavior
[14]. However, the high price of Rh restricts its industrial application.
Among these non-precious metal catalysts, FT synthesis catalysts
which are modied to synthesize higher alcohols are regarded as the
most promising candidates for higher alcohols synthesis [1517].
It is well known that Cu/Zn/Al or Cu/Zn/Al/Zr catalysts are usually
used to synthesize methanol from CO or CO2 hydrogenation [18
20].Over Cu-based catalysts, low content of higher alcohols are detected
in the liquid products, which led almost all researchers to explore the
addition of alkalis or some of FT elements (Fe, Co, Ni) to the catalysts
to increase the yield of higher alcohols. It is concluded that the formation of higher alcohols requires the dual active centers, which require
the synergism between Cu species and FT elements. The loss of synergism would destroy the active centers and lead to lower higher alcohols
selectivity. Nonetheless, in our previous study, it was found that the ethanol selectivity of Cu/Zn/Al catalysts without promoters could reach an
Corresponding author.
E-mail address: huangwei@tyut.edu.cn (W. Huang).

http://dx.doi.org/10.1016/j.fuproc.2016.01.005
0378-3820/ 2016 Elsevier B.V. All rights reserved.

unexpected point [21]. However, it was difcult to reproduce the former

results, even if some catalysts exhibited excellent ethanol selectivity,
which came up to approximately 40% at the initial stage of reaction,
but the ethanol selectivity sharply decreased to 5% after 120 h reaction
[22]. In addition, in our previous studies, we paid much attention to the
synergism of Cu0 and Cu+ as well as high Cu/Zn ratio of the catalysts,
whereas we did not notice the effect and variation of Al species.
Therefore, in the present work, a series of Cu/Zn/Al/Zr catalysts
were prepared with various atomic ratios of Al/Zr. The inuence of Al
and Zr on the catalytic performance was investigated and the catalysts
were characterized by X-ray diffraction (XRD), H2 temperatureprogrammed reduction (H2-TPR), temperature- programmed desorption of ammonia (NH3-TPD-MS), N2 adsorption, and X-ray photoelectron spectrometry (XPS).
2. Experiment
2.1. Catalyst preparation
The Cu/Zn/Al/Zr catalysts with Al/Zr atomic ratios of 4:1, 2:1 were
prepared by complete liquid-phase technology, and the Cu: Zn:
(Al + Zr) atomic ratio was kept at 2:1:0.8. Initially a certain amount of
citric acid was dissolved in distilled water, following by addition of Aluminum isopropoxide [(C3H7O)3Al] and Zr(NO3)25H2O, and the water
bath temperature maintained at 323 K for 3 h, then the mixture temperature was raised to 368 K and kept for 1 h. Next, Cu(NO3)23H2O and
Zn(NO3)26H2O were dissolved in glycol and the resulting solution
was slowly added to the Al/Zr solution. The resulting Cu/Zn/Al/Zr solution was stirred at 368 K until a homogeneous gel was obtained. The

Y.-J. Liu et al. / Fuel Processing Technology 144 (2016) 186190

gel was aged at room temperature for 10 days and dispersed in liquid
parafn, heated under N2 atmosphere from 333 K to 573 K at the rate
of 5 K/min and maintained for 8 h at 573 K. A slurry catalyst was subsequently obtained. The two catalysts were denoted as CAT-AZ(4:1),
CAT-AZ(2:1), respectively. Cu/Zn/Al catalyst omitted the addition of
zirconium nitrate was named as CAT-Al and Cu/Zn/Zr catalysts omitted
the addition of Aluminum isopropoxide was named as CAT-Zr.
2.2. Characterization of catalysts
Before catalyst characterization, the slurry catalysts were centrifuged, extracted with petroleum ether for 2 days, and dried at room
temperature, and then the solid samples were obtained.
XRD patterns were recorded on a Rigaku D/MAX-2500 Diffractometer in a 2 range of 585 with Cu K radiation (40 kV, 100 mA).
H2-TPR tests were carried out in a xed-bed reactor. For each TPR
test, the sample (50 mg) was purged with He (40 mL/min) at 423 K to
remove physically adsorbed water and other impurities, then it was reduced in a ow of 5 vol.% H2 + N2 (40 mL/min) at a heating rate of 10 K/
min up to 773 K. A thermal conductivity detector (TCD) was used to record the reduction peaks.
The acidity of the samples was measured by NH3-TPD-MS. The samples were rst reduced at 553 K in a ow of 5 vol.% H2 + N2 (40 mL/min)
for half an hour. After cooling to 323 K, the samples were saturated with
pure NH3 for 30 min and then ushed with He ow to remove all physical adsorbed molecules. After that, the TPD experiments were started
with a heating rate of 10 K/min under He ow (40 mL/min), and the
desorbed NH3 were detected by an AMETEK mass spectrometer.
The pore size distribution of samples was carried out by N2 adsorption at liquid nitrogen temperature 77 K, using a Micromeritics Quanta
chrome instrument. Samples degassing were carried out at 473 K
prior to acquisition of the adsorption isotherm.
X-ray photoelectron spectroscopy (XPS) measurements were conducted using an ESCALAB 250 spectrometer (VG Scientic Ltd., UK)
equipped with monochromated Al K (h = 1486.6 eV, 150 W)
under ultrahigh vacuum (7 108 Pa), The binding energies were calibrated by the C 1 s peak at 284.6 eV.
2.3. Catalytic activity test
CO hydrogenation was carried out in a continuous-ow, highpressure, 0.5 L slurry reactor under continuous mechanical agitation.
The catalyst was reduced with H2/N2 (75 mL/min, V(H2)/V(N2) =
1:4) under atmospheric pressure at 553 K for 8 h. After reduction, the
synthesis gas (H2/CO = 2) was introduced into the reactor under the reaction conditions of 523 K, 4.5 MPa with a feed ow rate of 150 mL/min.
The steady-state activity measurements were taken after the reaction of
24 h. The gaseous products were analyzed online with a gas chromatograph equipped with a thermal conductivity detector (TCD) to detect
H2, CO, CH4 and CO2 and a ame ionization detector (FID) to detect ethanol, methanol, DME, and hydrocarbon, respectively. The liquid products were collected daily and analyzed ofine using the gas
chromatograph. The CO conversion and the carbon-based for higher alcohols, methanol, DME, CO2 and hydrocarbon were calculated by an internal normalization method. Each data set was obtained from an
average of three independent measurements.

187

Table 1
The catalytic performance of catalysts with different Al/Zr atomic ratio.
Catalyst

CAT-Al
CAT-AZ(4:1)
CAT-AZ(2:1)
CAT-Zr

CO conversion
(%)
19.8
25.5
27.1
36.7

Selectivity (wt.%)
ROH

HC

DME

CO2

16.8
19.4
22.6
58.0

17.1
8.5
7.4
0.5

10.0
23.7
22.4
18.5

56.1
48.3
45.6
19.6

Methanol
(%)

C2+ OH
(%)

41.2
55.9
69.7
92.0

58.8
44.1
30.3
8.0

Notes: Reaction conditions: T = 523 K, P = 4.5 MPa, H2/CO = 2, feed low rate = 150 mL/
min, ROH for total alcohols and HC for hydrocarbon.

the CO conversion and total alcohols selectivity increased, whereas the

selectivity of higher alcohols and CO2 decreased notably, illustrating
that the introduction of Zr restrained the water-gas shift reaction and
lessened the formation of higher alcohols. The catalytic performance results showed that Al might favor the formation of higher alcohols. Fig. 1
showed the variation of higher alcohols selectivity of Cu/Zn/Al/Zr catalysts with time on stream (TOS). As seen in Fig. 1, the higher alcohols selectivity rst increased and then decreased after 72 h except for CAT-Zr
catalyst, illustrating that the catalysts had a process of induction and had
different degrees of deactivation. Remarkably, with Zr content increasing, the deactivation rate of the catalysts decreased, illustrating that Zr
was benecial to improve the stability of the catalyst. Thus, a suitable
Al/Zr atomic ratio for improving the stability of the catalysts and maintaining the selectivity of higher alcohols requires to be researched deeply in the future.
3.2. XRD characterization
The XRD patterns of the catalysts with different Al/Zr atomic ratio
before and after reaction were presented in Fig. 2. As seen in Fig. 2, all
catalysts exhibited similar diffraction lines of Cu0 and weakly ZnO, no
CuO and Cu2O were observed, which had been proved by our previous
work [23,24]. Metallic Cu0 appeared in the un-reduced catalysts was
due to the decomposition of liquid parafn which led to the reduction
of CuO species [25]. Moreover, it could be found that the diffraction
peaks of Cu0 became weaker with the increase of Zr content, illustrating
that Zr was benecial to improve the dispersion of Cu species of the catalysts. In addition, the diffraction peaks of ZrO2 could be detected only
for the CAT-Zr since the strong Cu0 diffraction peaks, which suggested
that Al and Zr species existed in an amorphous state. After reaction,
compared with Zr-containing catalysts, the diffraction peaks of Cu0
and ZnO for CAT-Al had changed signicantly, which further suggested
that Zr was benecial to the dispersion of Cu species.

3. Results and discussion

3.1. Catalytic performance
The catalytic performance of Cu/Zn/Al/Zr catalysts with different Al/
Zr atomic ratio toward CO hydrogenation was summarized in Table 1.
As shown in Table 1, the CAT-Al catalyst had lower CO conversion and
total alcohols selectivity. However, the selectivity of higher alcohols
(C2 + OH) reached approximately 58.8%. With Zr content increasing,

Fig. 1. The higher alcohols selectivity of catalysts with different Al/Zr atomic ratio. Reaction
conditions: T = 523 K, P = 4.5 Mpa, H2/CO = 2, Feed ow rate = 150 mL/min.

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Y.-J. Liu et al. / Fuel Processing Technology 144 (2016) 186190

second peak was attributed to Cu2O species which had strong interactions with zinc or aluminum oxide [22]. With Zr content increasing,
only a single reduction peak was detected. It was clearly seen that the
reduction peaks of Cu2O species obviously shifted to lower temperature,
which indicated that the Cu2O could be reduced more easily to Cu0 with
the increasing of Zr content. Moreover, the peak area of the CAT-Zr was
much bigger than that of Al-containing catalysts, suggesting that the
amount of reducible Cu2O of CAT-Zr was much more than that of Alcontaining catalysts. On the other hand, it could be seen from Fig. 3
that the interaction between Cu and Al of CAT-Al was the strongest,
which exhibited better catalytic activity toward higher alcohols. This result was in accordance with our previous experimental and theoretical
study results [22,26] and other researchers' results [9,27,28].
3.4. NH3-TPD-MS characterization
The acidity of Cu/Zn/Al/Zr catalysts with different Al/Zr atomic ratio
before and after reaction was detected by NH3-TPD. As shown in Fig. 4,
only one peak in the temperature range was observed for all catalysts
and this peak could be assigned to the dehydration of surface hydroxyl
groups [29]. It was noticed that the intensity of the peak decreased continuously with the increasing of Zr content, illustrating that the amount
of weak acid sites of Cu/Zn/Al/Zr catalysts decreased with the increasing
of Zr content. However, after reaction, the amount of weak acid sites of
catalysts decreased except for CAT-Zr, and the largest decline happened
on CAT-Al. Combined with the catalytic performance, the selectivity of
higher alcohols was in a good agreement with the amount of weak
acid sites, which illustrated that larger amount of weak acidic sites

Fig. 2. XRD patterns of catalysts with different Al/Zr atomic ratio. (a) Before reaction
(b) after reaction.

3.3. H2-TPR characterization

To investigate the reduction behavior of the Cu/Zn/Al/Zr catalysts,
the catalysts with different Al/Zr atomic ratio before reaction were carried out by TPR measurement. As shown in Fig. 3, there were two reduction peaks for CAT-Al catalyst, which was similar to our previous study.
The rst peak was assigned to the reduction of dispersed Cu2O, and the

Fig. 3. H2-TPR proles of catalysts with different Al/Zr atomic ratio before reaction.

Fig. 4. NH3-TPD-MS proles of catalysts with different Al/Zr atomic ratio. (a) Before
reaction (b) after reaction.

Y.-J. Liu et al. / Fuel Processing Technology 144 (2016) 186190

was benecial to the formation of higher alcohols. These results indicated that the amount of the weak acidic sites played a key role in the CO
hydrogenation to higher alcohols and the amount of weak acidic sites
decreasing might lead to the deactivation of catalysts. Therefore, controlling the surface acid sites constant and improving the stability of
the catalysts are needed to be studied further in the future.
3.5. N2 adsorption characterization
Fig. 5 showed the pore size distributions of different catalysts before
and after reaction. It could be seen that the pore size distribution curves
all showed a peak around 4 nm for all catalysts, indicating the catalysts
were comprised of mesoporous structure, which was also discovered by
our group [30]. After reaction, the most probable pore size increased to
6.5 nm and the peak of CAT-Al became widen, no obvious changes were
observed for Zr-containing catalysts. This result illustrated that Zr favored the stability of pore structure.
3.6. XPS characterization
The chemical state and surface components of the catalysts with different Al/Zr atomic ratio were characterized by XPS. And the surface
compositions of the catalysts before and after reaction were listed in
Table 2. As seen in Table 2, the Cu/Zn ratio increased overall with the increasing of Zr content before reaction. Combined with the aforementioned catalytic performance, CO conversion and total alcohols (ROH)
selectivity increased with the increasing of Zr content, which illustrated
that Cu species mainly acted as an active phase for hydrogen dissociation in the higher alcohols synthesis. The XPS characterization also
showed that the binding energy (BE) of Cu2p3/2 value of all catalysts before and after reaction was around 932.0 eV and no shake-up satellite
peaks in the range of 940.0 and 945.0 eV existed (seen in Fig. 6),

Fig. 5. Pore size distribution curves of catalysts with different Al/Zr atomic ratio. (a) Before
reaction (b) after reaction.

189

Table 2
The surface compositions of different Cu/Zn/Al/Zr catalysts.
Catalyst

CAT-Al
CAT-AZ(4:1)
CAT-AZ(2:1)
CAT-Zr

Before reaction

After reaction

Cu/Zn

Cu/Al

(Cu + Zn)/Al

Cu/Zn

Cu/Al

(Cu + Zn)/Al

0.27
0.24
0.38
1.16

0.07
0.07
0.09

0.32
0.32
0.33

0.20
0.13
0.15
1.47

0.07
0.03
0.06

0.42
0.29
0.47

indicating the absence of CuO species [31]. The Zn2p3/2 BE of all catalysts
before and after reaction was located at about 1021.5 eV and the corresponding Zn LMM Auger peak was at KE 987.5 eV, indicating Zn species
were present as ZnO. However, it should be pointed out that the BE of
Cu2p3/2 and Zn2p3/2 increased, whereas the BE of Al 2p decreased
after the addition of Zr (seen in Table 3), suggesting that the addition
of Zr changed the chemical surroundings of Cu, Zn and Al components,
which might reinforce the effect of Cu and Zn, whereas weakened the
effect of Al. The binding energy of Al 2p before and after reaction were
shown in Fig. 7. As seen in Fig. 7, the peaks of Al 2p shifted to lower binding energy after reaction for Al-containing catalysts, and the binding energy of CAT-Al declined sharply, which illustrated that the chemical
environment of Al in the catalyst had changed signicantly. The addition of Zr slowed down the decline of Al2p BE, illustrating that Zr
could make the surroundings of Al more stable and then improve the
stability of the catalytic performance.

4. Conclusion
The Cu/Zn/Al/Zr catalysts without alkalis and FT elements were
prepared by complete liquid-phase technology for higher alcohols synthesis from CO hydrogenation. The CAT-Al catalyst exhibited excellent
higher alcohols selectivity, reaching approximately 58.8%. With Zr/Al
atomic ratio increasing, the catalytic activity and stability increased,
but methanol became the main product in the liquid products over
Cu/Zn/Zr catalyst. Al favored the formation of higher alcohols and Zr
was benecial to improve the stability of catalysts. Based on the characterization results, it could be concluded that the addition of Zr improved
the dispersion of Cu, made the catalyst easier to be reduced, and decreased the amount of weak acidic sites. It was also concluded that the
amount of the weak acidic sites played a key role in the higher alcohols
formation and the decrease of weak acidic sites lead to the deactivation
of catalysts.

Fig. 6. Cu 2p spectra of catalysts with different Al/Zr atomic ratio before reaction.

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Y.-J. Liu et al. / Fuel Processing Technology 144 (2016) 186190

Table 3
The binding energy of catalysts with different Al/Zr atomic ratio.
Before reaction (eV)

After reaction (eV)

Catalyst
CAT-Al
CAT-AZ(4:1)
CAT-AZ(2:1)
CAT-Zr

Cu 2p3/2

Zn 2p3/2

Al 2p

Cu 2p3/2

Zn 2p3/2

Al 2p

932.0
932.2
932.1
932.4

1021.7
1022.0
1021.7
1021.1

74.5
74.1
74.2

932.2
932.6
932.1
932.5

1020.7
1021.8
1021.5
1021.2

73.4
73.8
73.8

Fig. 7. Al 2p spectra of catalysts with different Al/Zr atomic ratio. (a) CAT-Al; (b) CAT-AZ
(4:1); (c) CAT-AZ (2:1). (1) before reaction (2) after reaction.

Acknowledgments
This work was supported by Natural Science Foundation of China
(21176167); the Key Project of Natural Science Foundation of China
(21336006); and the Doctoral Program of Higher Education Priority
Development Areas (20111402130002).
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