Preparation of a new solid acid and its catalytic performance in di(1-naphthyl)methane hydrocracking

Article abstract of DOI:10.1016/S1872-2067(15)61112-3

A new solid acid was prepared by trifluoromethanesulfonic acid (TFMSA) impregnation into an acid-treated attapulgite (ATA). Di(1-naphthyl)methane (DNM) hydrocracking was used as the probe reaction to evaluate the catalytic performance of TFMSA/ATA for cleaving C_ar–C_alk bridged bonds in coals. The results show that DNM was specifically hydrocracked to naphthalene and 1-methylnaphthalene over TFMSA/ATA in methanol in the absence of gaseous hydrogen. In particular, TFMSA/ATA was demonstrated to be stable after four cycles with slight loss in catalytic activity. Furthermore, a proposed H⁺ transfer mechanism successfully interprets the TFMSA/ATA-catalyzed hydrocracking reaction of DNM.

Full text of DOI:10.1016/S1872-2067(15)61112-3

Chinese Journal of Catalysis 37 (2016) 1324–1330
a v a i l a b l e a t w w w . s c i e n c e d i r e c t . c o m
j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / c h n j c
Article
Preparation of a new solid acid and its catalytic performance in
di(1‐naphthyl)methane hydrocracking
Meixia Zhao, Xianyong Wei*, Zhimin Zong
Key Laboratory of Coal Processing and Efficient Utilization, Ministry of Education, China University of Mining & Technology, Xuzhou 221116, Jiangsu,
China
A R T I C L E I N F O
A B S T R A C T
Article history:
A new solid acid was prepared by trifluoromethanesulfonic acid (TFMSA) impregnation into an
acid‐treated attapulgite (ATA). Di(1‐naphthyl)methane (DNM) hydrocracking was used as the
probe reaction to evaluate the catalytic performance of TFMSA/ATA for cleaving Car–Calk bridged
bonds in coals. The results show that DNM was specifically hydrocracked to naphthalene and
1‐methylnaphthalene over TFMSA/ATA in methanol in the absence of gaseous hydrogen. In partic‐
ular, TFMSA/ATA was demonstrated to be stable after four cycles with slight loss in catalytic activi‐
ty. Furthermore, a proposed H+ transfer mechanism successfully interprets the TFMSA/ATA‐ cata‐
lyzed hydrocracking reaction of DNM.
Received 3 March 2016
Accepted 15 April 2016
Published 5 August 2016
Keywords:
Solid acid
Di(1‐naphthyl)methane
Hydrocracking
H+ transfer
© 2016, Dalian Institute of Chemical Physics, Chinese Academy of Sciences.
Published by Elsevier B.V. All rights reserved.
1. Introduction
gating coal‐related model compound (CRMC) reactions proved
to be a powerful approach for revealing molecular‐level DCL
With decreasing fossil fuel reserves and soaring energy de‐
mands, efficient utilization of coals has attracted tremendous
attention. Direct coal liquefaction (DCL) is a promising process
for producing clean liquid fuels and value‐added chemicals
[1−3]. In the DCL process, catalysts play crucial roles in cleav‐
ing C–C bonds and facilitating hydrogen transfer [4−6]. Liquid
acids such as trifluoromethanesulfonic acid (TFMSA) [7,8],
HF+BF3 [9], and molten salts [10] have been widely studied in
DCL. However, poor recyclability, strong corrosiveness, and the
serious environmental contamination issues restrict their in‐
dustrial applications.
mechanisms [11−13]. In recent years, signiꢀicant efforts have
been devoted to directional degradation of coals and CRMCs
over solid acids. Wang et al. [14] investigated the decomposi‐
tion of diphenylmethane and bibenzyl over sulfated zirconia.
The work suggested that the acidic property of the catalyst
contributed largely to CRMC bond rupture. Yue et al. [15] ex‐
amined the hydrocracking of di(1‐naphthyl)methane (DNM)
over a solid acid prepared by pentachloroantimony and trime‐
thylsilyl trifluoromethanesulfonate impregnation into an acti‐
vated carbon. The results showed that heterolytic cleavage of
H2 into H+ and H− was the key step for the cleavage of Car–Calk
bond in DNM. The aforementioned solid acids, although
effective, still require the use of pressurized hydrogen at ele‐
vated temperatures. Therefore, it is imperative to develop nov‐
Solid acids are environmentally benign and easily recycled
in comparison with liquid acids and have great promise as DCL
catalysts. Because of the complexity of coal structures, investi‐
* Corresponding author. Tel: +86‐516‐83885951; Fax: +86‐516‐83884399; E‐mail: wei_xianyong@163.com
This work was supported by the Fundamental Research Fund for the Central Universities (China University of Mining & Technology, 2014ZDPY34)
and the Priority Academic Program Development of Jiangsu Higher Education Institutions.
DOI: 10.1016/S1872‐2067(15)61112‐3 | http://www.sciencedirect.com/science/journal/18722067 | Chin. J. Catal., Vol. 37, No. 8, August 2016

Meixia Zhao et al. / Chinese Journal of Catalysis 37 (2016) 1324–1330
1325
el catalysts that allow cleaving the bridged bonds in coals under
mild conditions, especially in the absence of pressurized hy‐
drogen.
Catalyst supports play vital roles in improving catalytic ac‐
tivity and stability. Attapulgite is a type of hydrated magnesium
aluminum silicate having lath or fibrous morphology, being
desirable as a solid acid catalyst support because of its large
specific surface area, considerable porosity, and excellent
thermal stability [16].
In this study, a new solid acid was prepared using an ac‐
id‐treated attapulgite (ATA) as the support and TFMSA as the
active component. The catalytic performance of as‐prepared
TFMSA/ATA was investigated by cleaving Car–Calk bondin DNM
in the absence of H2. The potential cleavage route of DNM over
TFMSA/ATA was also deduced.
apparatus at –196 C. Samples were previously outgassed at
300 C for 5 h. NH3 temperature‐programmed desorption
(NH3‐TPD) was conducted on a TP‐5000 type multi‐function
adsorption instrument. The samples were pretreated at 650 C
for 1 h and then cooled to 100 C. The introduction of NH3 was
performed for 0.5 h followed by purification with He for 1 h to
remove physisorbed NH3. Desorption under He was performed
in the range of 100–800 C at 10 C/min to remove chemi‐
sorbed NH3. X‐ray photoelectron spectroscopic (XPS) meas‐
urements were determined using a Thermo Fisher ESCALAB
250Xi spectrophotometer with the Al K radiation with a beam
spot size of 900 m (energy step size 1.000 eV, pass energy
50.0 eV). Accurate binding energies were determined by refer‐
ence to the C 1s peak at 284.5 eV.
2.4. Catalytic reactions
2. Experimental
DNM (1 mmol), catalyst (0–40 mg), and methanol (10 mL)
were added into a 60‐mL stainless steel and magnetically
stirred autoclave. The autoclave was purged with N2 and pres‐
surized to 1 MPa at room temperature before heating to a de‐
sired temperature (260–320 C). After reaction at a specific
temperature for a prescribed period of time (0.5–5 h), the au‐
toclave was immediately quenched to room temperature in an
ice‐water bath before filtering the reaction mixture. The filtrate
was analyzed using an Agilent 7890/5975 gas chromato‐
graph/mass spectrometer (GC/MS) equipped with a capillary
column coated with HP‐5MS (60 m × 0.25 mm × 0.25 m) and a
quadrupole analyzer operated in electron impact (70 eV) mode.
The capillary column was heated from 60 to 300 C at 10
C/min and held at 300 C for 6 min. The relative content of
each compound was determined by normalizing peak area, i.e.,
the peak area of the compound divided by the sum of the peak
areas of all the identified compounds in the total ion chroma‐
togram. Quantitative analysis was performed using DNM as an
external standard during analysis with GC/MS. Furthermore,
each experiment, under the same conditions, was repeated at
least three times to minimize DNM conversion and product
yield errors to less than ±1%.
2.1. Materials
Attapulgite powder (AP) was purchased from Jiangsu
Huahong Mining Chemical Co., Ltd., Xuyi, China. DNM is an ana‐
lytical reagent purchased from Heowns Chemical Co., Ltd.,
Tianjin, China. Both methanol and TFMSA were purchased from
Aladdin Industrial Inc., Shanghai, China. Methanol was purified
by distillation prior to use.
2.2. Catalyst preparation
AP was treated in 0.5 mol/L HCl aqueous solution under re‐
flux with vigorous agitation for 4 h. Thereafter, the suspension
was filtered and washed with distilled water until Cl was un‐
detectable by silver nitrate titration. The filter cake was dried
under vacuum at 110 C for 6 h to obtain ATA, which was then
ground and sieved to 100–200 mesh size. TFMSA/ATA was
prepared by impregnation, i.e., TFMSA (5 mL) was added
dropwise into ATA (2 g) under a N2 atmosphere followed by
refluxing at 90 C for 8 h. The mixture was cooled, filtered,
washed with acetone, and calcined at 350 C for 12 h. TFMSA
loaded on ATA is ca. 14.7%, which was calculated according to
the mass change. Besides TFMSA/ATA, TFMSA/γ‐Al2O3 and
TFMSA/ZSM‐5 were also prepared under the same conditions.
3. Results and discussion
As Fig. 1 shows, ATA exhibits ordered fibrous morphology
and a smooth surface with diameters between 20 and 30 nm.
Conversely, the surface characteristics of TFMSA/ATA differ
from ATA in which a rough surface is observed. Another dif‐
ferent surface feature is the presence of irregular grains with
diameters < 10 nm that are relatively uniformly distributed on
the ATA surface without obvious aggregation. Among the de‐
tected elements, O, Mg, Al, and Si are mainly attributed to the
ATA framework, while K and Fe most likely arise from impuri‐
ties in the parent ATA. Additionally, F and S from TFMSA were
also detected in TFMSA/ATA (Fig. 2). Energy‐dispersive spec‐
trometric (EDS) analysis demonstrates a F content of 5.2 wt%
on TFMSA/ATA, which is close to the F loading (5.6%) calcu‐
lated according to the mass difference between added ATA and
the resulting TFMSA/ATA.
2.3. Catalyst characterization
Transmission electron microscopic (TEM) observation of
ATA and TFMSA/ATA and corresponding elemental analysis
were performed using a JEM‐1011 JEOL microscope operating
at 200 kV coupled to an energy‐dispersive spectrometric de‐
tector. Fourier transform infrared (FTIR) analysis was per‐
formed using a Nicolet Magna IR‐560 spectrometer with a res‐
olution of 4 cm−1 over the spectral range of 4000–400 cm−1
using KBr pellets. X‐ray diffraction (XRD) patterns were rec‐
orded on a Bruker D8 Advance diffractometer with Cu K radi‐
ation ( = 1.5406 Å) at 40 kV and 30 mA in the 2θ range of
3–80. Specific surface area, pore volume, and average pore
size of the samples were measured using an Autosorb‐1‐MP

1326
Meixia Zhao et al. / Chinese Journal of Catalysis 37 (2016) 1324–1330
(a)
(b)
Fig. 1. TEM images of ATA (a) and TFMSA/ATA (b).
As Fig. 3 illustrates, there are significant differences in FTIR
spectra among AP, ATA, and TFMSA/ATA. The absorbance at
3616 cm−1 is ascribed to the –OH stretching vibration in dioc‐
tahedral coordination, while the band at 3550 cm−1 is attribut‐
ed to the –OH stretching vibration of adsorbed water coordi‐
nated to Al and Mg at the edges of the channels [17].The band
at 1630 cm−1 results from the bending vibration of zeolitic wa‐
ter [18]. The characteristic absorbances at 1015 and 801 cm−1
are assigned to Si–OR and Si–O–Si bonds, respectively [19].
Noteworthily, the absorbance of carbonates at 1451 cm−1 from
ATA and TFMSA/ATA is much weaker than that from AP, indi‐
cating that the majority of carbonates in AP were removed by
acid treatment. The FTIR spectrum of TFMSA/ATA displays
additional bands at 1255 and 1173, 1035, and 614 cm−1, which
correspond to symmetric and asymmetric stretching vibrations
of the S=O bond, C–F stretching vibrations, and C–S bending
vibrations, respectively [20]. These results evidently indicate
that TFMSA was successfully loaded on ATA.
sis. The atomic density of F is ca. 4.40% on the surface of
TFMSA/ATA (Table 1), which is consistent with EDS analysis
(Fig. 2). The F 1s spectrum of TFMSA/ATA is fitted with four
distinct peaks related to the various bonding configurations of
F atoms in TFMSA/ATA. Specifically, the strong peak located at
687.8 eV is assigned to the F–Al bond [21]. The peak at 688.8
eV is attributed to the F–C bond [22], while the peaks centered
at 685.1 and 686.8 eV result from F–Mg and F–Si bonds [23,24],
respectively. These results are indicative of the interaction be‐
tween ATA and supported TFMSA.
As Fig. 5 demonstrates, there are appreciable differences in
the XRD patterns among AP, ATA, and TFMSA/ATA. The peaks
at 8.5, 16.9, and 33.6 can be ascribed to the characteristic
diffraction peaks of AP, representing the (110), (040), and
(400) planes, respectively, while those at 13.7, 20.0, and 21.1
can be attributed to the Si–O–Si crystalline layers in AP [25,26].
The peak at 24.6 can be indexed to the diffraction from quartz
as an impurity [27] and its intensity from ATA is much weaker
than that from AP, further indicating that the impurity was
effectively removed by acid treatment. Compared with ATA, the
diffraction peaks of TFMSA/ATA at 8.5, 16.9, and 33.6 are
weak or broad, implying that the crystalline structure was sig‐
nificantly destroyed by TFMSA loading.
As Fig. 4 exhibits, the existence of C, F, S, and O along with
other elements in TFMSA/ATA is further verified by XPS analy‐
ATA
Si
Element
wt %
at %
O K
46.4
6.2
60.1
5.3
Only a single desorption peak at 358.3 C was observed in
the NH3‐TPD profile of ATA (Fig. 6), which can be assigned to
the desorption of NH3 from medium‐strength Lewis acid sites
on ATA [28]. Compared with ATA, TFMSA/ATA displays two
Mg K
Al K
Si K
K K
5.5
4.2
O
40.3
0.5
29.7
0.3
Mg
Al
K
Fe
Fe K
1.1
0.4
0
1
2
3
4
5
6
7
C
TFMSA/ATA
Element
C K
wt %
34.1
at %
44.7
TFMSA/ATA
O K
40.0
2.8
39.3
1.8
1.2
7.5
Si
Mg K
Al K
Si K
2.0
ATA
AP
O
13.4
Mg
Al
S K
F K
2.5
5.2
1.2
4.3
S
F
4000
3500
3000
2500
2000
1500
1000
500
Wavenumber (cm-1)
0
1
2
3
4
5
6
7
Energy (keV)
Fig. 3. FTIR spectra of AP, ATA, and TFMSA/ATA.
Fig. 2. Energy dispersive spectra of ATA and TFMSA/ATA.

Meixia Zhao et al. / Chinese Journal of Catalysis 37 (2016) 1324–1330
1327
s
TFMSA/ATA
F 1
measured
fitting
687.8
688.8
685.1
686.8
1200 1000 800
600
400
200
0
682
684
686
688
692
690
Binding energy (eV)
Binding energy (eV)
Fig. 4. XPS spectra of TFMSA/ATA.
lene were detected in the mixtures from DNM hydrocracking,
while the resulting formaldehyde from methanol dehydrogena‐
tion cannot be detected as it was drawn out together with the
solvent during analysis with GC/MS. The results show that both
DNM conversion and product yields increase with raising tem‐
perature, increasing TFMSA/ATA feed, and prolonging time;
however, DNM conversion almost reached 100% at 300 C over
40 mg TFMSA/ATA for 3 h. Interestingly, the yield of naphtha‐
lene is significantly higher than that of 1‐ methylnaphthalene,
indicating significant demethylation of 1‐methylnaphthalene.
The difference in naphthalene and 1‐methylnaphthalene yields
also increases with raising temperature, increasing
TFMSA/ATA feed, and prolonging time. The data suggest that
TFMSA/ATA selectively catalyzes DNM hydrocracking and de‐
methylation of the resulting 1‐methylnaphthalene. The activity
of TFMSA/ATA for DNM hydrocracking is significantly higher
Table 1
Atomic densities of main elements on the surface of TFMSA/ATA.
Element
Al 2p
Si 2p
S 2p
Binding energy (eV)
74.04
Atomic density (%)
1.13
7.62
1.31
102.70
168.55
C ls
O 1s
F 1s
284.17
531.94
687.86
44.11
39.67
4.40
Mg 1s
1304.82
1.76
desorption peaks at 245.1 and 615.2 C, indicating the presence
of weak and strong acid sites on TFMSA/ATA, respectively.
Much stronger acid sites created after supporting TFMSA are
tentatively attributed to the interaction of supported TFMSA
with ATA, which is responsible for donating H+.
Table 2 shows that the specific surface area (278 m2/g) of
ATA is significantly larger than that (169 m2/g) of AP, favoring
the subsequent TFMSA loading. The decrease in specific surface
area and increase in pore size for ATA after TFMSA loading
imply that the majority of TFMSA was anchored to the channels
of ATA, expanding the pore size to some extent.
245.1
615.2
ATA
358.3
As Fig. 7 exhibits, only naphthalene and 1‐methylnaphtha‐
AP
TFMSA/ATA
quartz
AP
100
200
300
400
Temperature (oC)
Fig. 6. NH3‐TPD profiles of ATA and TFMSA/ATA.
500
600
700
800
ATA
Table 2
Physicochemical properties of AP, ATA, and TFMSA/ATA.
TFMSA/ATA
Specific surface area Pore volume Average pore size
Sample
(m2/g)
169
(cm3/g)
0.29
(nm)
4.60
7.55
7.92
10
20
30
40
50
60
70
80
AP
o
/
2 ( )
ATA
278
0.50
TFMSA/ATA
156
0.27
Fig. 5. XRD patterns of AP, ATA, and TFMSA/ATA.

1328
Meixia Zhao et al. / Chinese Journal of Catalysis 37 (2016) 1324–1330
100
Supported TFMSA 40 mg, 300 oC, 3 h
100
90
80
70
60
50
100
90
80
70
60
50
80
60
40
20
0
TFMSA/ATA 30 mg, 3 h
260
270
280
290
300
310
320
-Al2O3
ZSM-5
ATA
Temperature (oC)
Support
100
80
60
40
20
0
100
80
60
40
20
0
Fig. 8. DNM conversion over different supported TFMSA.
between ATA and supported TFMSA favors the release of H+
from TFMSA/ATA. The attack of H+ from TFMSA/ATA on the
ipso‐position of DNM leads to the formation of naphthalene and
naphth‐1‐ylmethylium, as demonstrated in Scheme 1. Subse‐
quently, H− abstraction from methanol by the resulting
naphth‐1‐ylmethylium proceeds, resulting in 1‐methylnaph‐
thalene and formaldehyde along with the release of H+. The
released H+ subsequently induces DNM hydrocracking or
1‐methylnaphthalene demethylation.
300 oC, 3 h
0
10
20
30
40
TFMSA/ATA feed (mg)
Commercial viability requires excellent catalyst stability,
therefore catalytic recycling tests conducted on TFMSA/ATA
were performed. As exhibited in Fig. 9, DNM conversion slightly
decreases with increasing recycle times, indicating good stabil‐
ity of the catalyst. The slight decrease of DNM conversion may
be related to carbon deposition. The NH3‐TPD profile of the
recycled TFMSA/ATA catalyst suggests that there is no appre‐
ciable loss in acidity for the spent catalyst. The above evidence
indicates that TFMSA/ATA presents excellent stability.
100
85
70
55
40
25
100
85
70
55
40
25
TFMSA/ATA 30 mg, 300 o
C
H
O
-
O
S
O
S
0
1
2
3
4
5
O
F
O
F
F
F
F
Time (h)
+ H+
F
O
Fig. 7. Effects of temperature, TFMSA/ATA feed, and time on DNM
hydrocracking.
TFMSA/ATA
H+
than that of either TFMSA/γ‐Al2O3 or TFMSA/ZSM‐5 under the
same conditions (Fig. 8). The outstanding catalytic perfor‐
mance displayed by TFMSA/ATA is not only attributed to its
large specific surface area but is also related to the synergic
effect between ATA and the supported TFMSA.
The dissociation energy of Car–Calk bond in DNM was re‐
ported to be 355.6 kJ/mol, therefore thermal cleavage of the
Car–Calk bond in DNM at 300 C is extremely difficult [29]. Hy‐
drogen transfer either from H• or H+ greatly facilitates Car–Calk
bond cleavage, as the attack of H• or H+ on the ipso‐position of
an aromatic ring connected to methylene yields a stable arene
rather than a labile aryl radical in addition to a relatively stable
leaving group, i.e., an arylmethyl radical or arylmethylium
[30,31]. Analysis of TFMSA/ATA suggests that the interaction
+
H
H
+
+
CH3OH
+
HCHO
+
H+
CH4
H+
+
+
+
CH3OH
+CH3
HCHO
+
H+
Scheme 1. Possible mechanism for DNM hydrocracking over
TFMSA/ATA.

Meixia Zhao et al. / Chinese Journal of Catalysis 37 (2016) 1324–1330
1329
100
80
60
40
20
0
TFMSA/ATA 30 mg, 300 oC, 3 h
(a)
234.2
(b)
606.5
0
1
2
3
4
100 200 300 400 500 600 700 800
Temperature (oC)
Recycle times
Fig. 9. DNM conversion over fresh and recycled TFMSA/ATA (a) and NH3‐TPD profile of TFMSA/ATA after 4‐times of recycles (b).
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4. Conclusions
Near 100% hydrocracking of DNM to naphthalene and
1‐methylnaphthalene over TFMSA/ATA at 300 C in methanol
in the absence of gaseous hydrogen was observed, suggesting
that TFMSA/ATA exhibits excellent catalytic activity for the
cleavage of Car–Calk bridged bonds under mild conditions. The
catalytic mechanism of DNM hydrocracking over TFMSA/ATA
is ascribed to the preference of the catalyst to promote H+
transfer to the ipso‐position of DNM. No obvious deactivation
was observed even after several cycles. The TFMSA/ATA cata‐
lyst provides a promising new route for preparing similar cata‐
lysts applied in coal conversions.
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Graphical Abstract
Chin. J. Catal., 2016, 37: 1324–1330 doi: 10.1016/S1872‐2067(15)61112‐3
Preparation of a new solid acid and its catalytic performance
in di(1‐naphthyl)methane hydrocracking
methanol TFMSA/ATA
300 oC
N2
Meixia Zhao, Xianyong Wei*, Zhimin Zong
China University of Mining & Technology
ATA
TFMSA
A new solid acid catalyst prepared by trifluoromethanesulfonic
acid (TFMSA) impregnation into an acid‐treated attapulgite (ATA)
specifically hydrocracked di(1‐naphthyl)methane to naphthalene
and 1‐methylnaphthalene over TFMSA/ATA at 300 C in methanol
without gaseous hydrogen.
H
O
O
S
O
F
F
F
(a)
TFMSA/ATA

1330
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