View Article Online / Journal Homepage / Table of Contents for this issue

Green Chemistry
PAPER

Efficient dehydration of bio-based 2,3-butanediol to

Cite this: Green Chem., 2012, 14, 3441 butanone over boric acid modified HZSM-5 zeolites
Wengui Zhang,a Dinghua Yu,a,b Xiaojun Jia and He Huang*a,b
Published on 29 October 2012 on http://pubs.rsc.org | doi:10.1039/C2GC36324K

The dehydration of bio-based 2,3-butanediol provides an alternative green way to produce butanone,
which is mainly produced through the dehydrogenation of butanol in industry. In this research, the
effect of the framework Si/Al ratio on 2,3-butanediol dehydration over HZSM-5 zeolites (Si/Al = 38–360)
Downloaded by University of Sussex on 06 December 2012

Received 22nd August 2012,
Accepted 27th October 2012
DOI: 10.1039/c2gc36324k
www.rsc.org/greenchem
was investigated. HZSM-5(360) was further modified with boric acid, and the influence of the loading
amount of boric acid on the dehydration performance was studied. The results showed that high Si/Al
ratio was beneficial to low-temperature activation of 2,3-butanediol and the methyl migration to
2-methyl propanal. 1.0%B/HZSM-5(360) not only showed best performance at 180 °C but also kept
stable activities between 180–300 °C with a high LHSV 2.4 h−1. According to the characterization results,
excellent performance over HZSM-5(360) was due to the highest amount of strong acidic sites
(1.1674 mmol g−1) attributed to H-bonded hydroxyl groups, normally silanols. Coexistence of more
effective extraframework B–OH species and retained silanols were responsible for the promotion of cata-
lytic performance over 1.0%B/HZSM-5(360).

1. Introduction
During the last few years, considerable efforts and progresses
have been made for the production of bio-based chemicals
from renewable resources as the price of petrochemical
feedstocks continuously increases and their availability
diminishes.1–5 As one typical bio-based diol, 2,3-butanediol
(2,3-BDL) can be derived from the bio-conversion of various
resources, such as glucose,6,7 sucrose,8 glycerol9 and mixture
of glucose and xylose10 etc. For its attractive high yield (more
than 130 g L−1),11 fermented 2,3-BDL is an excellent platform
compound for expanding a network of bio-based chemicals
through catalytic technologies.12–15 Among the technologies,
catalytic dehydration is always considered as an effective way
to develop downstream products from bio-based polyatomic Scheme 1 Main products of 2,3-butanediol dehydration.
alcohols.16–18 Through the dehydration of 2,3-BDL,8,10 some
bulk chemicals, such as butanone (methyl ethyl ketone, MEK), competitive green way but needs the R&D of efficient catalysts.
butadiene (DBE) and 2-methyl propanal (MPA) etc., could be In the reported literature,12–15,22 solid materials such as
produced (see Scheme 1). oxides, clay, aluminum silicates and liquid sulfuric acid were
As an excellent organic solvent for resins and lacquers, mainly studied for the dehydration. Ohara and Furuhashi12
MEK is mainly produced through the dehydrogenation of found that the MEK yield was 50–60% of the theoretical
butanol in industry, originally from hydration of petroleum between 300–450 °C over catalysts such as acid oxides, clay and
butylenes.19–21 The dehydration of 2,3-BDL provides a aluminum silicates. Neish et al.14 utilized 3–20% of H2SO4 as
the catalyst and developed a continuous process by using con-
ditions that favor removal of the cyclic ketal from the reaction
a
College of Biotechnology and Pharmaceutical Engineering, Nanjing University of mixture. These catalysts above showed high activities in the
Technology, Nanjing 210009, Jiangsu, P. R. China. E-mail: biotech@njut.edu.cn;
dehydration, but there were still some disadvantages, such
Tel: +86-25-83172094
b
State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing as high reaction temperature over the solid catalysts and
University of Technology, Nanjing 210009, Jiangsu, P. R. China corrosiveness of sulfuric acid.

This journal is © The Royal Society of Chemistry 2012 Green Chem., 2012, 14, 3441–3450 | 3441
 Paper
Recently, some materials such as synthetic zeolites and het-
eropoly acids have been studied for the dehydration of 2,3-
BDL.23–27 Molnar et al.23 introduced zeolites of types X and Y
as catalysts in diols dehydration at an atmospheric pressure at
230–350 °C. Toeroek et al.24 utilized various heteropoly acids
in the reaction and found that the selectivity depended on the
acid strength and the form of them. Lee et al.25 studied differ-
ential reaction of 2,3-BDL dehydration over ZSM-5, mordenite,
β and Y zeolites using in situ DRIFTS, and found that MEK for-
mation was favored on ZSM-5 but aldol condensation and ulti-
mately aromatization narrowed the window of practical utility.
Zhang et al.27 made some efforts to drive the application of
HZSM-5 zeolites in the dehydration through modification with
Published on 29 October 2012 on http://pubs.rsc.org | doi:10.1039/C2GC36324K
Fe2(SO4)3/H2SO4. The Fe/HZSM-5 zeolites (Si/Al = 20–30)
showed good dehydration performances. However, the
reported research about ZSM-5 zeolites mainly focused on
those with low Si/Al ratios. Importantly, detailed effects of
Downloaded by University of Sussex on 06 December 2012
acidic sites on dehydration activities over the zeolites have still
never been revealed.
Boric acid and its salts were considered as green catalysts in
many acid-catalyzed reactions,28–30 and always used in improv-
ing the catalytic performance of zeolites.31–33 Compared with
metallic sulfates or nitrates, boric acid is much greener for
modification of zeolites without emission of decomposed com-
pounds, such as SOx and NOx, during calcination. Especially,
boric acid could effectively activate the ortho hydroxyl
groups.28 In this research, the effect of framework Si/Al ratio
on 2,3-BDL dehydration over HZSM-5 zeolites (Si/Al = 38–360)
was investigated. Zeolite HZSM-5 (Si/Al = 360) was further
modified with boric acid, and the influence of loading amount
of boric acid on the dehydration performance was studied.
Combining with characterization technologies, such as XRD,
BET, FTIR, and NH3-TPD, we aimed at revealing the main
active surface species and their effects on the catalytic
activities. This work will be helpful with understanding the
mechanism of 2,3-BDL dehydration over HZSM-5 and develop-
ing efficient green catalysts for the production of bio-based
MEK.
2. Experimental
2.1 Catalyst preparation
HZSM-5 zeolites with various Si/Al ratios (38, 50, 100, 120, 200
and 360, respectively) were obtained from Catalyst Factory of
Nankai University, named as “HZSM-5(Si/Al ratio)”. Boron
modified zeolites were prepared by incipient wetness impreg-
nation as follows: zeolite HZSM-5(360) powder was mixed
together with the boric acid and water, and placed at room
temperature for 24 hours. The amount of boric acid was quan-
tified by the reduced content of boron oxide (0.5 wt%, 1.0 wt%,
2.0 wt%, 4.0 wt%, 6.0 wt% and 8.0 wt%, respectively).
The volume of water was 40 mL per 10 g zeolite powder.
The mixtures were then dried at 120 °C for 4 hours, calcined
from 120–550 °C at a heating rate of 10 °C min−1, holding
for 4 hours at 550 °C. The samples were cooled to
3442 | Green Chem., 2012, 14, 3441–3450
Green Chemistry
View Article Online
room temperature under ambient conditions, tableted and
crushed into 30–40 meshes, named as “content%B/HZSM-5
(360)”.
2.2 Catalyst test and product analysis
The dehydration of 2,3-BDL to MEK over the catalysts was
tested in a fixed-bed quartz reactor of 8 mm inner diameter.
Catalysts (1.5 g) with 30–40 meshes were charged in the
middle section of the reactor, with quartz wool packed in both
ends. Before catalytic evaluation, the catalyst was pretreated at
the required reaction temperature for 0.5 hour under high-
purity N2 (0.1 MPa, 12.5 mL min−1). Then the feedstock, an
aqueous solution of 2,3-BDL (60 wt%), was pumped into the
preheating zone first (input speed = 6 mL h−1) driven through
the catalyst bed by nitrogen (0.1 MPa, 12.5 mL min−1). The
diol was purified from a fermentation process containing
78.8% meso and 21.2% racemic isomers.
The liquid products during 60–90 min were condensed and
collected in a trap, then weighed and analyzed. The value of
recovered mass/injected mass kept around 80–95 wt%. The
analysis was carried out off-line by a Shimadzu GC-2010 gas
chromatograph using a TCD detector equipped with a Stabil-
wax-DA capillary column (30 m, ID 0.32 mm, film thickness
0.25 μm). The injector and detector temperature was 280 and
300 °C, respectively. The oven was kept at 70 °C for 2 minutes,
then raised to 170 °C at a rate of 10 °C min−1 where it
remained for 2 minutes, then finally raised to 215 °C at 15 °C
min−1 and remained for 2 minutes. The flow of hydrogen used
as a carrier gas was 32.8 mL min−1. By the way, in the long-
term test, the catalytic performance was determined by analy-
zing the liquid sample collected for 30 minutes before the set
time.
Ethanol (EO) was used as the internal standard substance.
The conversion of 2,3-BDL and the selectivities of the main
products (shown in Scheme 1) were calculated as follows:
msample output  mH2 O output  mBDL output
BDL Conv: ¼
msample output  mH2 O output
 100% ð1Þ
mMEK output
MEK Sel: ¼  100% ð2Þ
msample output  mBDL output  mH2 O
mMPA output
MPA Sel: ¼  100% ð3Þ
msample output  mBDL output  mH2 O
mDBE output
DBE Sel: ¼  100% ð4Þ
msample output  mBDL output  mH2 O
The symbol of msample output means that the weight of the
output liquid sample, and the weights of compounds in the
liquid sample, including butanone (MEK), methyl propanal
(MPA), butadiene (DBE), water and unreacted feed 2,3-BDL,
were calculated through the equation:
mi ¼
Ai
 fmði=ethanolÞ  methanol ð5Þ
Aethanol
This journal is © The Royal Society of Chemistry 2012
 Green Chemistry Paper
View Article Online

The fm(i/ethanol) values of 2,3-BDL, water, MEK, MPA, and a thin round piece. The piece was then scanned in the range
DBE were 1.2249, 0.7024, 1.1934, 1.1585 and 1.0488, 400–4000 cm−1.
respectively.

2.3 Catalyst characterization

XRD (X-ray diffraction) analysis was carried out on a Thermo
ARL X’TRA X-ray diffractometer from Thermo Electron Corpor-
ation using Cu Kα radiation. The Kα1 wavelength was
0.15406 nm. The intensity data were collected at 25 °C in a 2θ
range 5–75° with a scanning speed of 5° min−1.
N2 physical adsorption/desorption measurements were
carried out on an ASAP2020 instrument from Micromeritics.
Published on 29 October 2012 on http://pubs.rsc.org | doi:10.1039/C2GC36324K
3. Results and discussion
3.1 Catalytic performance
3.1.1 EFFECT OF SI/AL RATIO ON DEHYDRATION PERFORMANCES OVER
HZSM-5 ZEOLITES. Undoubtedly, the dehydration of 2,3-butane-
diol should be affected by the surface acid properties of
HZSM-5 zeolites. For the unmodified H-zeolites, acid proper-
ties are determined by their Si/Al ratios of frameworks. There-

Before the measurements, the catalysts were vacuumed for
10 hours, 4 hours at 300 °C and 325 °C. The micropore width
was obtained from the Horvath–Kawazoe method, and the
specific surface area and micropore volume were calculated by
Downloaded by University of Sussex on 06 December 2012
fore, we investigated the dehydration behavior of bio-2,3-BDL
over the zeolites with various Si/Al ratios, and the correspond-
ing results are listed in Table 1. At 200 °C, the conversion of
2,3-BDL was improved by the increasing Si/Al ratio, while the

Brunauer–Emmet–Teller (BET) method and t-plot method,34
respectively.
NH3-TPD (temperature-programmed desorption of
ammonia) was performed by the BEL-CAT-B-82 instrument
connected to a thermal conductivity detector. Sample
(0.1000 g) in a quartz reactor was heated in a flow of helium to
550 °C at a rate of 20 °C min−1 and maintained at this temp-
erature for 60 minutes. The ammonia (or carbon dioxide) was
adsorbed at 120 °C for 60 minutes, and the sample was then
flushed with the flow of helium at 120 °C for 40 minutes. TPD
of ammonia was performed at a helium flow of 40 mL min−1
and a heating rate of 10 °C min−1 from 120–750 °C. The acid
amount was determined by integrating the TPD curve in the
temperature range.
FT-IR (Fourier transformed infrared spectroscopy) was
carried out on an Avatar 360 FT-IR spectrometer from Nicolet
using DTGS KBr as detector and KBr as the beam splitter. The
catalyst was mixed together with KBr powder and tableted into
selectivity ratio of MEK to MPA substantially decreased. From
HZSM-5(38) to HZSM-5(360), the conversion of 2,3-BDL was
improved from 24.4% to 90.9%, while the value of MEK/MPA
decreased from 12.1 down to 4.9. When the reaction temp-
erature reached up to 300 °C, all the conversion of 2,3-BDL
reached 100.0%, and the selectivities of MEK were around
66.1%–72.1%, while the value of MEK/MPA kept around
2.4–2.8. Totally speaking, 2,3-BDL conversion and MPA selec-
tivity over HZSM-5 zeolites were effectively influenced by their
Si/Al ratios, especially under low reaction temperature.
HZSM-5(360) exhibited an excellent performance with high
conversion of 2,3-BDL and stable MEK selectivity.
In this research, MPA formation was found as the main
competitive reaction during the 2,3-BDL dehydration to MEK
over HZSM-5 zeolites. It was also observed over heteropolyacids
in the diol conversion,24 but was never referred to over
reported ZSM-5 zeolites.25–27 According to the proposed mech-
anism by Toeroek et al.,24 the formations of MEK and MPA

Table 1 Catalytic performance over HZSM-5 zeolites with various Si/Al ratios

Si/Al ratio Temp. (°C) BDL conv. (wt%) MEK sel. (wt%)a MPA sel. (wt%) DBE sel. (wt%) MEK/MPA

38 200 24.4 ± 0.8 69.0 ± 0.5 5.0 ± 0.5 0.0 12.1

250 97.3 ± 0.5 71.5 ± 0.4 20.5 ± 0.4 0.6 ± 0.05 3.5
300 100.0 ± 0.2 72.1 ± 0.4 26.6 ± 0.3 0.7 ± 0.04 2.7
50 200 21.9 ± 1.2 64.8 ± 0.6 6.3 ± 0.5 0.3 ± 0.06 10.3
250 100.0 ± 0.1 68.5 ± 0.5 24.1 ± 0.5 0.9 ± 0.04 2.8
300 100.0 ± 0.1 68.7 ± 0.4 29.1 ± 0.4 1.0 ± 0.04 2.4
100 200 29.0 ± 1.0 69.8 ± 0.8 8.7 ± 0.9 0.0 8.0
250 79.4 ± 0.7 68.2 ± 0.6 18.6 ± 0.6 0.8 ± 0.06 3.7
300 100.0 ± 0.1 70.1 ± 0.4 25.0 ± 0.4 0.6 ± 0.03 2.8
120 200 51.1 ± 0.9 66.4 ± 1.0 11.1 ± 0.8 0.6 ± 0.06 6.0
250 100.0 ± 0.1 68.9 ± 0.4 22.4 ± 0.3 1.2 ± 0.07 3.1
300 100.0 ± 0.1 68.8 ± 0.3 28.5 ± 0.3 1.0 ± 0.06 2.4
200 200 84.5 ± 0.5 69.9 ± 0.6 14.4 ± 0.4 0.6 ± 0.09 4.9
250 97.7 ± 0.3 75.1 ± 0.4 19.6 ± 0.5 1.0 ± 0.06 3.8
300 100.0 ± 0.1 70.3 ± 0.3 25.4 ± 0.3 0.7 ± 0.04 2.8
360 200 90.9 ± 0.5 68.3 ± 0.4 18.9 ± 0.3 1.5 ± 0.04 3.6
250 100.0 ± 0.1 66.1 ± 0.5 26.3 ± 0.4 1.5 ± 0.05 2.5
300 100.0 ± 0.1 69.4 ± 0.4 28.6 ± 0.4 1.0 ± 0.03 2.4
a
Note: The unlisted by-products were mainly composed of 2-methyl propanal, 3,4,5-trimethyl-2-cyclopentenone, tetramethylfuran and
3-hydroxy-2-butanone.

This journal is © The Royal Society of Chemistry 2012 Green Chem., 2012, 14, 3441–3450 | 3443
 Paper Green Chemistry
View Article Online
Published on 29 October 2012 on http://pubs.rsc.org | doi:10.1039/C2GC36324K

Scheme 2 MEK and MPA formation routes over acid catalyst.

Downloaded by University of Sussex on 06 December 2012

Table 2 Catalytic performance over B/HZSM-5(360) zeolites with various B2O3 contents

B2O3 content (wt%) Temp. (°C) BDL conv. (wt%) MEK sel. (wt%)a MPA sel. (wt%) DBE sel. (wt%) MEK/MPA

0 180 32.7 ± 1.0 73.8 ± 0.7 14.6 ± 0.8 0 5.1

200 90.9 ± 0.5 68.3 ± 0.4 18.9 ± 0.3 1.5 ± 0.04 3.6
0.5 180 90.6 ± 0.7 69.1 ± 0.4 15.0 ± 0.3 1.0 ± 0.07 4.6
200 100.0 ± 0.1 71.4 ± 0.5 18.9 ± 0.4 1.0 ± 0.08 3.8
1.0 180 97.2 ± 0.8 68.4 ± 0.5 16.8 ± 0.2 1.2 ± 0.1 4.1
200 100.0 ± 0.2 69.7 ± 0.4 20.1 ± 0.2 1.4 ± 0.1 3.5
2.0 180 36.6 ± 1.0 73.4 ± 0.6 13.2 ± 0.7 0.0 5.5
200 86.8 ± 0.9 67.3 ± 0.4 16.3 ± 0.5 0.7 ± 0.06 4.1
4.0 180 45.6 ± 1.1 71.6 ± 0.7 18.3 ± 0.8 0.2 ± 0.07 3.9
200 72.4 ± 0.8 70.3 ± 0.5 21.4 ± 0.7 0.4 ± 0.05 3.3
6.0 180 21.4 ± 1.2 78.3 ± 0.8 17.2 ± 0.9 0.0 4.6
200 67.8 ± 0.9 73.1 ± 0.7 22.2 ± 0.7 0.5 ± 0.07 3.3
8.0 180 11.9 ± 1.3 73.1 ± 0.9 12.5 ± 1.1 0.0 5.8
200 32.2 ± 1.0 75.6 ± 0.7 15.7 ± 0.9 0.0 4.8
a
Note: The unlisted by-products were mainly composed of 2-methyl propanal, 3,4,5-trimethyl-2-cyclopentenone, tetramethylfuran and
3-hydroxy-2-butanone.

should proceed by a pinacol rearrangement (shown in
Scheme 2), and racemic and meso favored in generating MEK
and MPA, respectively. However, the feedstock we used con-
tained 78.8% meso and 21.2% racemic isomers, while MEK
selectivities were dominant around 68%, and the highest MPA
selectivity was just 29.1%. It seems that racemic and meso
isomers of 2,3-BDL in the dehydration over HZSM-5 zeolites
favored in generating MPA and MEK, respectively. Combined
with the reaction results (see Table 1), we predict that the
increase of Si/Al ratios enhanced methyl migration, leading to
the increase of MPA selectivities. High Si/Al ratio is beneficial
to the activation of 2,3-BDL, which was more obvious under
low temperature.
3.1.2 EFFECT OF BORIC ACID AMOUNT ON DEHYDRATION PERFORMANCES
OVER B/HZSM-5(360) ZEOLITES. The dehydration of 2,3-BDL to
MEK could be described as a pinacol rearrangement.35
Reported in the literature,33 boron zeolites gave much
better selectivity than aluminum zeolites in aldehyde/ketone
rearrangements. Therefore, various amounts of boric acid were
introduced onto HZSM-5(360) zeolites for the diol dehydration,
and the related results are listed in Table 2. The conversion of
2,3-BDL increased with increasing B2O3 content and then
declined after 1.0%. 1.0%B/HZSM-5(360) exhibited the highest
conversion of 2,3-BDL (up to 97.2%) at 180 °C. Meanwhile, the
conversion over the parent HZSM-5(360) was just 32.7%. When
the content of B2O3 reached up to 8.0%, the modified catalyst
showed low conversion (only 11.9%). The selectivities of MEK
didn’t exhibit an obvious change with increasing B2O3 content
over the zeolites, keeping at around 70%. The highest MEK
selectivity (78.3%) occurred over 6.0%B/HZSM-5(360) at
180 °C. The MPA selectivities didn’t show an obvious tendency
with the increase of B2O3 content over the zeolites, whose
lowest value (12.5%) occurred over 8.0%B/HZSM-5(360) at
180 °C. The DBE selectivities kept at a low level, less
than 1.5%, over the zeolites. Overall, sparing modification
with boric acid (B2O3 < 1.0%) would greatly improve low-
temperature activity of the dehydrations over HZSM-5(360)
zeolites.

3444 | Green Chem., 2012, 14, 3441–3450 This journal is © The Royal Society of Chemistry 2012
 Green Chemistry
Published on 29 October 2012 on http://pubs.rsc.org | doi:10.1039/C2GC36324K
Fig. 1 Catalytic performance over 1.0%B/HZSM-5(360): (a) results at various temperatures for 90 min, (b) lifetime curve at 180 °C.
Downloaded by University of Sussex on 06 December 2012
Fig. 2 XRD patterns of HZSM-5 zeolites with various Si/Al ratios.
1.0%B/HZSM-5(360) exhibited high activity at a low reaction
temperature. To get more detailed catalytic behavior, its per-
formance at various temperatures and lifetime at 180 °C were
also investigated, and the results are shown in Fig. 1. As shown
in Fig. 1a, the selectivities of MEK remained stable around
70%, while the MPA selectivities steadily increased with
increasing reaction temperature. The conversions of 2,3-BDL
also stayed at a high level, near or up to 100%. As shown in
Fig. 1b, the activity of 1.0%B/HZSM-5(360) could be retained
for more than 78 hours. In other words, this catalyst is very
suitable for industrial application in the dehydration of 2,3-
BDL for its high activity and wide operation window of temp-
erature. It must be mentioned that the selectivities of MEK
kept stable at around 70% over the B/HZSM-5(360) zeolites.
It means that the modification of boric acid can affect the
activation of 2,3-BDL but can’t effectively adjust product
distribution.
3.2 Catalyst characterization
3.2.1 STRUCTURE AND TEXTURE PROPERTIES. XRD patterns of
HZSM-5 zeolites with various Si/Al ratios were characterized
and are shown in Fig. 2. With the increase of Si/Al ratio, the
This journal is © The Royal Society of Chemistry 2012
Paper
View Article Online
Fig. 3 XRD patterns of B/HZSM-5(360) zeolites with various B2O3 contents.
peak intensity of crystal plane (011) is enhanced, while the
peak intensities of crystal planes (501), (051) and (133) are
both weakened. The peak positions of the zeolites are nearly
the same. It means that Si/Al ratio can affect the structure of
the zeolites, increasing Si/Al ratio increases the occupancy of
low index surfaces such as (011).
The XRD patterns of B/HZSM-5(360) zeolites with various
B2O3 contents were also characterized, in order to get infor-
mation on structural changes after loading boric acid (shown
in Fig. 3). The peak positions in the patterns are nearly the
same, and no new peaks occurred. The intensity of the peaks
shows a continual decline with increasing load of boric acid. It
means that no crystalline boron species can be observed, but
the crystallinity of the zeolite is affected by the introduction of
boron. We predict that boron species are well dispersed over
the zeolite surface during the loading, and might undergo
some reaction with the zeolite surface or framework.
According to the XRD results, there was no pronounced
structure difference between HZSM-5 zeolites and modified
HZSM-5 zeolites with boron. The little differences can’t explain
the remarkable difference in catalytic performance over them.
Therefore, we also carried out N2 physical adsorption/
Green Chem., 2012, 14, 3441–3450 | 3445
 Paper Green Chemistry
View Article Online

desorption measurements, and the results are listed in
Table 3. As shown in Table 3, the parent HZSM-5 zeolites with
various Si/Al ratios show similar surface areas, pore volumes
and pore widths. With increasing B2O3 content, the values
of texture characteristics show a minor decline. The value
decrease might be attributed to the coverage of zeolite surface
by boron species.
3.2.2 SURFACE ACID PROPERTIES. The dehydration activities of
the catalysts are always controlled by surface acid properties.
NH3-TPD is a typical technology to distinguish distribution
and determine the amount of acidic sites over solid
Published on 29 October 2012 on http://pubs.rsc.org | doi:10.1039/C2GC36324K
catalysts.36–38 NH3-TPD profiles of HZSM-5 zeolites with
various Si/Al ratios are shown in Fig. 4, and the corresponding
detailed results are listed in Table 4. NH3-TPD of B/HZSM-5
(360) zeolites with various B2O3 contents were also charac-
terized, the profiles and the detailed results are shown in
Fig. 5 and Table 5, respectively.
As shown in Fig. 4, the profiles of the unmodified zeolites
are remarkably different from each other. The first and second
desorption peaks (Peak 1 and Peak 2) slightly move to a lower
temperature, and the peak area decreases with increasing Si/Al
ratio. The third desorption peaks (Peak 3) of HZSM-5(200) and
HZSM-5(360) are obviously higher than the others. According
to the detailed results in Table 4, it can be found that the total

Table 3 Texture characteristics of parent and modified HZSM-5 zeolites

acid amounts of the zeolite substantially decrease with increas-
SBET Vmicro Pore width ing Si/Al ratios. The decrease is mainly due to the decline of
Catalysts (m2 g−1) (cm3 g−1) (nm) acid amount corresponding to Peak 1 and Peak 2, which
always belong to the weak and medium acidic sites, respect-
Downloaded by University of Sussex on 06 December 2012

HZSM-5(38) 318 0.20 0.5598

HZSM-5(50) 314 0.19 0.5615 ively. The amount of strong acidic sites corresponding to Peak
HZSM-5(100) 312 0.21 0.5589 3 substantially increases with increasing Si/Al ratios. HZSM-5
HZSM-5(120) 319 0.20 0.5620 (360) had the lowest total acid amount but the highest amount
HZSM-5(200) 316 0.22 0.5617
HZSM-5(360) 325 0.21 0.5641 of strong acidic sites, whose values were 1.6579 mmol g−1 and
0.5%B/HZSM-5(360) 326 0.22 0.5637 1.1674 mmol g−1, respectively.
1.0%B/HZSM-5(360) 322 0.21 0.5640 As shown in Fig. 5, it can be observed that the peak areas of
2.0%B/HZSM-5(360) 310 0.19 0.5635
4.0%B/HZSM-5(360) 298 0.18 0.5568 Peak 1 desorbed during 100–200 °C increase with increasing
6.0%B/HZSM-5(360) 290 0.18 0.5559 B2O3 contents over B/HZSM-5(360) zeolites. The medium and
8.0%B/HZSM-5(360) 288 0.17 0.5528 strong acid sites, corresponding to Peak 2 and Peak 3,

Fig. 4 NH3-TPD profiles of HZSM-5 zeolites with various Si/Al ratios. Fig. 5 NH3-TPD profiles of B/HZSM-5(360) zeolites with various B2O3 contents.

Table 4 NH3-TPD results of HZSM-5 zeolites with various Si/Al ratios

Peak temperature (°C) Desorbed NH3 amount (mmol g−1)

Total acid amount
Si/Al ratio Peak 1 Peak 2 Peak 3 Peak 1 Peak 2 Peak 3 (mmol g−1)

38 163.9 337.3 571.9 1.6359 1.6172 0.3818 3.6349

50 160.6 334.4 577.9 1.4282 1.6789 0.4278 3.5349
100 164.1 339.1 576.9 1.0527 1.1667 0.3644 2.5838
120 152.2 327.8 572.4 0.5956 0.9072 0.2844 1.7872
200 149.0 291.7 576.6 0.7570 0.4397 0.8224 2.0191
360 138.5 297.0 580.9 0.1757 0.3148 1.1674 1.6579

3446 | Green Chem., 2012, 14, 3441–3450 This journal is © The Royal Society of Chemistry 2012
 Green Chemistry Paper
View Article Online

Table 5 NH3-TPD results of B/HZSM-5(360) zeolites with various B2O3 contents

Peak temperature (°C) Desorbed NH3 amount (mmol g−1)

B2O3 content Total acid amount
(wt%) Peak 1 Peak 2 Peak 3 Peak 1 Peak 2 Peak 3 (mmol g−1)

0 138.5 297.0 580.9 0.1757 0.3148 1.1674 1.6579

0.5 146.9 319.2 587.6 0.2496 0.2594 0.5804 1.0894
1.0 136.3 305.5 583.3 0.3129 0.2923 0.3586 0.9638
2.0 131.2 286.8 582.7 0.3157 0.2444 0.2196 0.7797
4.0 141.8 273.0 583.7 0.6508 0.2215 0.3337 1.1960
6.0 147.9 276.8 588.3 0.8732 0.2439 0.3508 1.4679
8.0 128.3 266.8 575 1.1990 0.1856 0.3520 1.7366
Published on 29 October 2012 on http://pubs.rsc.org | doi:10.1039/C2GC36324K
Downloaded by University of Sussex on 06 December 2012

Fig. 6 FTIR spectra of HZSM-5 zeolites with various Si/Al ratios: (a) absorption during 3900–1500 cm−1, (b) transmission during 1300–400 cm−1.

respectively, are obviously weakened with the increasing con-
tents. When the content reaches more than 4.0%, the second
desorbed peaks become unobvious in the profiles. According
to the detailed results in Table 5, the total acid amount
of B/HZSM-5(360) zeolites decreases with increasing B2O3
content below 2.0% and then increases. The amount of strong
acidic sites shows the same tendency. For weak acidic sites cor-
responding to Peak 1, their amount increases with increasing
B2O3. Meanwhile, the amount of medium acidic sites doesn’t
show an obvious tendency. The values are mostly around
0.22 mmol g−1.
In the NH3-TPD curves of H-zeolites, the peaks observed
above 400 °C are generally attributed to the desorption of NH3
from strong Brönsted and Lewis sites, which are of catalytic
importance.39 On the other hand, the low-temperature peaks
can be attributed to a number of causes: (a) desorption of
weakly adsorbed NH3 on weak acid sites or non-acidic site,
(b) weak acid Brönsted and Lewis sites, and (c) formation
of NH4+(NH3)n (n ≥ 1) groups.40 Over unmodified HZSM-5
zeolites, the conversions of 2,3-BDL showed an obvious
increase with increasing Si/Al ratios at 200 °C. Coincident with
the catalytic results, the amount of strong acidic sites corres-
ponding to Peak 3 substantially increases with increasing Si/Al
ratios. Thereby, we speculate that the strong acidic sites are
mainly responsible for the dehydration activity of 2,3-BDL over
these unmodified HZSM-5 zeolites. It might be attributed to
efficient protonation of hydroxyl groups of 2,3-BDL by the
strong acidic sites, which is always considered as the key step
of the diol dehydration (see Scheme 2).
However, over the boron modified HZSM-5(360) zeolites,
the catalytic results can’t be clearly explained according to the
relative TPD results. The best catalysts 0.5%B/HZSM-5(360)
and 1.0%B/HZSM-5(360) zeolites exhibited a low amount of
strong acidic sites (0.5804–0.3586 mmol g−1) and total acid
amount (1.0894–0.9638 mmol g−1). These values were less
than those of unmodified HZSM-5(360) zeolites. Therefore, the
dehydration performance can’t only be explained by the
amount of acidic sites and their distribution. It was reported
that boron zeolites gave much better selectivity than alumi-
num zeolites in aldehyde/ketone rearrangements.33 Especially,
boric acid could effectively activate the ortho hydroxyl
groups,28 but over B/HZSM-5(360) zeolites the boron species
might not exist in the form of boric acid after the calcination.
Therefore, the form of boron species and their effects on cata-
lytic activities must be considered.
FTIR technologies were carried out to investigate the
surface differences after modification of boric acid over
HZSM-5(360) zeolites and unmodified HZSM-5 zeolites with
various Si/Al ratios. The FTIR spectra of HZSM-5 and
B/HZSM-5(360) zeolites are shown in Fig. 6 and 7, respectively.
Fig. 6a shows the absorption spectra during 3900–1500 cm−1.
A pronounced band near 3668 cm−1 is observed, which is due

This journal is © The Royal Society of Chemistry 2012 Green Chem., 2012, 14, 3441–3450 | 3447
 Paper
Published on 29 October 2012 on http://pubs.rsc.org | doi:10.1039/C2GC36324K
Fig. 7 FTIR spectra of B/HZSM-5(360) zeolites with various B2O3 contents: (a) absorption during 3900–1600 cm−1, (b) transmission during 1300–400 cm−1.
Downloaded by University of Sussex on 06 December 2012
to the presence of a small amount of extraframework Al–OH
species on the zeolites.41 That HZSM-5(360) zeolite exhibits an
unobvious band near 3668 cm−1 indicates the low surface
Al–OH content on it. Except for HZSM-5(360), the other zeo-
lites show a weak broad band near 3511 cm−1, always assigned
to internal silanols. Meanwhile, a pronounced broad band
near 3500 cm−1 is found in HZSM-5(360), due to H-bonded
hydroxyl groups in defect sites, which is typically found in the
case of silicalite S1.41 The results observed in Fig. 6a confirm
that there are more active Si–OH sites and fewer extraframe-
work Al species in the zeolites with higher Si/Al ratio,
especially over HZSM-5(360).
Fig. 6b shows the transmission spectra from 1300–400 cm−1
of the unmodified zeolites. The bands near 802, 1064 and
1228 cm−1 are characteristic of SiO4 tetrahedron units.41,42 The
strong band in the region 1000–1300 cm−1 is assigned to the
internal vibration of SiO4, AlO4 tetrahedra for ZSM-5. The band
around 1064 cm−1 is attributed to the internal asymmetric
stretching vibration of Si–O–T linkage.42 As shown in Fig. 6b,
the asymmetric stretching vibration peaks at 1228 and
1064 cm−1 generally shift to higher wavenumbers with increas-
ing Si/Al ratio. This shift is due to the slightly lower mass of
aluminum compared to that of silicon. The band near
802 cm−1 is assigned to the symmetric stretching of the exter-
nal linkages, and the strong band near 545 cm−1 is attributed
to the double five-ring lattice vibration of the external lin-
kages.41,42 The band at around 445 cm−1 is due to the T–O
bending vibrations of the SiO4 and AlO4 internal tetrahedra.
The bands around 545 and 445 cm−1 are characteristic of the
ZSM-5 crystalline structure.
Fig. 7 shows the FTIR spectra of B/HZSM-5(360) zeolites
with various B2O3 contents (calculated contents). To dis-
tinguish the boron species well, the FTIR of H3BO3 was also
carried out but is not shown in Fig. 7. Its characteristic bands
are near 547, 648, 784, 834, 926, 1027, 1193, 1457, 2260, 2362,
2514 and 3219 cm−1. In the spectra of B/HZSM-5(360) zeolites,
the characteristic bands of H3BO3, such as 648, 1193, 2260,
2362 and 2514 cm−1, are not found (see Fig. 7). It means that
3448 | Green Chem., 2012, 14, 3441–3450
Green Chemistry
View Article Online
the form of boron species on the zeolite surface can’t be
H3BO3, which might decompose during the calcination at
550 °C.
As shown in Fig. 7a, the band near 3679 cm−1, which dis-
appeared over pure HZSM-5(360), is refound in B/HZSM-5(360)
zeolites. This band near 3679 cm−1 is due to the presence of
extraframework species on the zeolites,41 while the band of
pure HZSM-5 zeolites are near 3668 cm−1, lower than
3679 cm−1. We predict that the species corresponding to the
band near 3679 cm−1 might be extraframework B–OH
species.32 The broad weak bands near 3498 cm−1 are observed
in the B/HZSM-5(360) zeolites, attributed to the H-bonded
hydroxyl groups in defect sites, normally silanols. A pro-
nounced sharp band near 3220 cm−1 is observed in the spectra
of 8.0%B/HZSM-5(360), while the other modified zeolites
exhibit weak and broad bands in the region. This might be
due to occurrence of hydrated boron oxide species on the
zeolite with a high loading amount of boric acid, which might
be generated from the decomposition of boric acid during the
calcinations.32
Fig. 7b shows the transmission spectra of B/HZSM-5(360)
zeolite in the region 1300–400 cm−1. The spectra in the region
are nearly the same as the spectra of pure HZSM-5(360). The
bands near 1085 cm−1 generally shift to lower wavenumbers
with increasing B2O3 contents. The bands are attributed to the
internal asymmetric stretching vibration of the Si–O–T
linkage.42 The occurrence of the band near 3679 cm−1 and this
shift might be attributed to the reaction of boric acid with
zeolite surface silanols. This surface reaction can also be
demonstrated by the decline of XRD peak intensities and
surface areas with increasing load amount of boric acid (see
Fig. 3 and Table 3).
According to the literature32,43 and characterization results,
silanol groups and extraframework B–OH species, considered
as the effective acidic sites, co-exist on the surface of
B/HZSM-5(360) zeolites. Especially, the generation of effective
B–OH species always goes with the disappearance of more
silanols, such as 1 mol of Si–O–B(OH)–O–Si groups generate
This journal is © The Royal Society of Chemistry 2012
 Green Chemistry
from 1 mol of boric acid and 2 mol of silanol. The coverage or
reaction of silanols would bring on the decline in the amount
of strong acidic sites (see Table 5). Compared with silanols,
B–OH species possess better protonation ability, leading to
higher temperatures of Peak 3 in NH3-TPD of B/HZSM-5(360)
zeolites (see Fig. 5 and Table 5). However, the amount of
surface B–OH species was limited because of limited amount
of loading boric acid and the surface reactions. The minor
difference of corresponding signal (3679 cm−1) over B/HZSM-5
zeolites might be attributed to it (see Fig. 7).
As we know, the dehydration performance depends on two
factors: the amount and the strength of the effective acidic
sites. The amount of effective sites depends on the total
Published on 29 October 2012 on http://pubs.rsc.org | doi:10.1039/C2GC36324K
amount of B–OH species and silanols (strength: B–OH species
> silanols). For the B/HZSM-5(360) zeolites (B2O3 amount less
than 1.0%), the coverage of silanols was acceptable with the
generation of effective B–OH species. As the reaction results,
Downloaded by University of Sussex on 06 December 2012
the activities in diol dehydration over the modified zeolites
were obviously improved. But for those modified zeolites (B2O3
amount more than 6.0%), the generation of B–OH species
accompanied by the covering of a large amount of original sila-
nols lead to the sharp decline of silanol sites (effective sites).
As the result, the conversion of 2,3-BDL over the modified zeo-
lites (B2O3 amount more than 6.0%) was very low. Overall,
excellent performance over HZSM-5(360) was due to the
highest amount of strong acidic sites (1.1674 mmol g−1),
where the active sites might be the H-bonded hydroxyl groups
in defect sites, normally silanols. The coexistence of more
effective extraframework B–OH species and retained silanols in
suitable amounts were responsible for the promotion of cataly-
tic performance over 0.5%B/HZSM-5(360) and 1.0%B/HZSM-5
(360).
4. Conclusions
High Si/Al ratio was beneficial to low-temperature activation of
2,3-butanediol and the methyl migration to 2-methyl propanal,
leading to a high yield of butanone and high selectivity for
2-methyl propanal. HZSM-5(360) exhibited the highest yield of
butanone (62.1%) and highest selectivity for 2-methyl propanal
(18.9%) at 200 °C. Sparing modification with boric acid (B2O3
< 1.0%) obviously enhanced the performance of HZSM-5(360).
1.0%B/HZSM-5(360) not only showed the highest conversion at
180 °C but also kept stable activities at higher temperatures
(up to 300 °C) with a high LHSV of 2.4 h−1. The conversion of
2,3-butanediol and selectivity for butanone over 1.0%B/
HZSM-5(360) could reach up to 97.2% and 68.4% at 180 °C,
respectively. According to the characterization results, excellent
performance over HZSM-5(360) was due to the highest amount
of strong acidic sites (1.1674 mmol g−1), where the active sites
might be the H-bonded hydroxyl groups in defect sites, nor-
mally silanols. Coexistence of more effective extraframework
B–OH species and retained silanols with suitable amounts
were responsible for the promotion of catalytic performance
over 1.0%B/HZSM-5(360).
This journal is © The Royal Society of Chemistry 2012
Paper
View Article Online
Acknowledgements
The authors thank the financial support by the National
Science Foundation for Distinguished Young Scholars of
China (No. 21225626), the National Key Technology R&D
Program (No. 2012BAD32B08), the National Basic Research
Program (No. 2011CB710806), the National High Technology
R&D Program of China (No. 2011AA021207), the National
Natural Science Foundation of China (No. 20906051), and the
PHD Programs Foundation of Ministry of Education of China
(No. 20113221110010).
References
1 P. Azadi, R. Carrasquillo-Flores, Y. J. Pagan-Torres,
E. I. Guerbuez, R. Farnood and J. A. Dumesic, Green Chem.,
2012, 14, 1573–1576.
2 X. J. Ji, H. Huang, Z. K. Nie, L. Qu, Q. Xu and G. T. Tsao,
Adv. Biochem. Eng./Biotechnol., 2012, 128, 199–224.
3 G.-Q. Chen and M. K. Patel, Chem. Rev., 2011, 112, 2082–
2099.
4 L. Soh and J. Zimmerman, Green Chem., 2011, 13, 1422–
1429.
5 B. G. Hermann, K. Blok and M. K. Patel, Environ. Sci.
Technol., 2007, 41, 7915–7921.
6 J. A. Gao, H. Xu, Q. J. Li, X. H. Feng and S. Li, Bioresour.
Technol., 2010, 101, 7076–7082.
7 X. J. Ji, H. Huang, J. Du, J. G. Zhu, L. J. Ren, N. Hu and
S. Li, Bioresour. Technol., 2009, 100, 3410–3414.
8 L. Y. Zhang, Y. L. Yang, J. A. Sun, Y. L. Shen, D. Z. Wei,
J. W. Zhu and J. Chu, Bioresour. Technol., 2010, 101, 1961–
1967.
9 K. Petrov and P. Petrova, Appl. Microbiol. Biotechnol., 2009,
84, 659–665.
10 X. J. Ji, H. Huang, J. Du, J. G. Zhu, L. J. Ren, S. Li and
Z. K. Nie, Bioresour. Technol., 2009, 100, 5214–5218.
11 X. J. Ji, H. Huang and P. K. Ouyang, Biotechnol. Adv., 2011,
29, 351–364.
12 K. Ohara and S. Furuhashi, Nippon Nogei Kagaku Kaishi,
1942, 18, 143–150.
13 A. C. Neish, Can. Chem. Process Ind., 1944, 28, 862–866.
14 A. C. Neish, V. C. Haskell and F. J. Macdonald, Can. J. Res.,
1945, 23B, 281–289.
15 M. Winfield, J. C. S. I. R. (Aust.), 1945, 18, 412–413.
16 A. Yamaguchi, N. Hiyoshi, O. Sato and M. Shirai, Green
Chem., 2011, 13, 873–881.
17 J. Wang, W. Xu, J. Ren, X. Liu, G. Lu and Y. Wang, Green
Chem., 2011, 13, 2678–2681.
18 B. Katryniok, S. Paul, M. Capron, C. Lancelot, V. Belliere-
Baca, P. Rey and F. Dumeignil, Green Chem., 2010, 12,
1922–1925.
19 D. R. Fang, W. Z. Ren, Z. M. Liu, X. F. Xu, L. Xu, H. Y. Lu,
W. P. Liao and H. M. Zhang, J. Nat. Gas Chem., 2009, 18,
179–182.
Green Chem., 2012, 14, 3441–3450 | 3449
 Paper
20 S. Lambert, C. Cellier, F. Ferauche, E. M. Gaigneaux and
B. Heinrichs, Catal. Commun., 2007, 8, 2032–2036.
21 Z. L. Wang, H. C. Ma, W. C. Zhu and G. J. Wang, React.
Kinet. Catal. Lett., 2002, 76, 271–279.
22 A. N. Bourns and R. V. V. Nicholls, Can. J. Res., 1947, 25B,
80–89.
23 A. Molnar, I. Bucsi and M. Bartok, Acta Phys. Chem., 1985,
31, 571–579.
24 B. Toeroek, I. Bucsi, T. Beregszaszi, I. Kapocsi and
A. Molnar, J. Mol. Catal. A: Chem., 1996, 107, 305–311.
25 J. Lee, J. B. Grutzner, W. E. Walters and W. N. Delgass,
Stud. Surf. Sci. Catal., 2000, 130C, 2603–2608.
26 H. Huang, J. Yan, X. Ji, S. Li and Y. Hu, CN Pat,
Published on 29 October 2012 on http://pubs.rsc.org | doi:10.1039/C2GC36324K
101293817A, 2008.
27 J. Zhang, Y. Xie, K. Cheng, Y. Zhou, H. Liu and D. Liu, CN
Pat., 101580462A, 2009.
28 T. S. Hansen, J. Mielby and A. Riisager, Green Chem., 2011,
Downloaded by University of Sussex on 06 December 2012
13, 109–114.
29 B. Q. Xu, S. B. Cheng, S. Jiang and Q. M. Zhu, Appl. Catal.,
A, 1999, 188, 361–368.
30 C. T. W. Chu, G. H. Kuehl, R. M. Lago and C. D. Chang,
J. Catal., 1985, 93, 451–458.
31 V. R. R. Marthala, Y. Jiang, J. Huang, W. Wang, R. Gläser
and M. Hunger, J. Am. Chem. Soc., 2006, 128, 14812–
14813.
3450 | Green Chem., 2012, 14, 3441–3450
Green Chemistry
View Article Online
32 G. P. Heitmann, G. Dahlhoff, J. P. M. Niederer and
W. F. Hölderich, J. Catal., 2000, 194, 122–129.
33 M. W. Simon, S. S. Nam, W. Q. Xu, S. L. Suib, J. C. Edwards
and C. L. O’Young, J. Phys. Chem., 1992, 96, 6381–6388.
34 B. C. Lippens and J. H. de Boer, J. Catal., 1965, 4, 319–323.
35 R. Emerson, M. Flickinger and G. Tsao, Ind. Eng. Chem.
Prod. Res. Dev., 1982, 21, 473–477.
36 C. V. Hidalgo, H. Itoh, T. Hattori, M. Niwa and
Y. Murakami, J. Catal., 1984, 85, 362–369.
37 D. Ma, W. Zhang, Y. Shu, X. Liu, Y. Xu and X. Bao, Catal.
Lett., 2000, 66, 155–160.
38 L. Rodríguez-González, F. Hermes, M. Bertmer,
E. Rodríguez-Castellón, A. Jiménez-López and U. Simon,
Appl. Catal., A, 2007, 328, 174–182.
39 F. Lónyi and J. Valyon, Microporous Mesoporous Mater.,
2001, 47, 293–301.
40 G. Tonetto, J. Atias and H. de Lasa, Appl. Catal., A, 2004,
270, 9–25.
41 T. Armaroli, L. J. Simon, M. Digne, T. Montanari,
M. Bevilacqua, V. Valtchev, J. Patarin and G. Busca, Appl.
Catal., A, 2006, 306, 78–84.
42 L. Shirazi, E. Jamshidi and M. R. Ghasemi, Cryst. Res.
Technol., 2008, 43, 1300–1306.
43 C. Fild, H. Eckert and H. Koller, Angew. Chem., Int. Ed.,
1998, 37, 2505–2507.
This journal is © The Royal Society of Chemistry 2012