SCIENCE CHINA

Chemistry
• ARTICLES • April 2015 Vol.58 No.4: 738–746
doi: 10.1007/s11426-014-5199-3

Highly selective and stable hydrogenation of heavy

aromatic-naphthalene over transition metal phosphides
Muhammad Usman, Dan Li, Chunshan Li* & Suojiang Zhang*
Beijing Key Laboratory of Ionic Liquids Clean Process, State Key Laboratory of Multiphase Complex Systems,
Institute of Process Engineering, University of Chinese Academy of Sciences, Beijing 100190, China

Received March 31, 2014; accepted April 25, 2014; published online November 11, 2014

The present study reports a highly selective and stable catalytic approach for producing tetralin, an important chemical, solvent,
and H2 storage material. Transition metal phosphides (MoP, Ni2P, Co2P, and Fe2P) were prepared by wet impregnation and
temperature-programmed reduction and characterized by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy
(EDX), EDX mapping, scanning electron microscopy (SEM), transmission electron microscopy (TEM), brunauer-emmett-
teller (BET), temperature-programmed desorption of ammonia (NH3-TPD), and fourier transform infrared spectroscopy of
pyridine (pyridine-FTIR). Of all the transition metal phosphides MoP was formed at a lower reduction temperature, which re-
sulted in smaller particle size that enhanced the overall surface area of the catalyst. The existence of weak, moderate, and
Lewis acidic sites over MoP were responsible for its high tetralin selectivity (90%) and stability during the 100 h reaction
on-stream in a fixed-bed reactor.

coal tar, naphthalene, transition metal phosphides, selective hydrogenation, tetralin

1 Introduction phalt, and aromatic hydrocarbons (HCs); as dye solvent

carriers in the textile industry; as insecticides for fabric
moths and a larvicide for mosquitoes; and as intermediates
Environmental legislation and the need for efficient conver-
in the production of agricultural chemicals (e.g., carbaryl,
sion of coal-based raw materials into fine chemicals and
napropamide, and 1-naphthoxyacetic acid). Moreover, pure
fuels have resulted in increased interest in the development
hydrogen can be effectively produced from tetralin and can
of new hydroprocessing catalysts. Coal tar is a major feed
be used as an efficient hydrogen donor in fuel cells. Each
stock of various chemicals and carbon-based materials.
application has specific secondary uses [1–3].
Naphthalene, the major component of coal tar, can be used
The selective hydrogenation of naphthalene requires bi-
as a starting material for the production of tetralin and de-
functional catalysts with both metal and acid sites; high
calin. These chemicals are in high demand by many indus-
hydrogen pressure and temperatures are ideal for HCs con-
tries throughout the world with an annual production/
version [4,5]. Noble metals, including Rh, Ru, Ir, Pt, Pd/Pt,
importation in millions of pounds. Tetralin and decalin are
and Pt/Ir, show good activity and selectivity [6–13]. How-
extensively used as industrial solvents, primarily for fats,
ever, the high cost and low abundance of these metals hin-
resins, oils, and waxes; as substitutes for turpentine in lac-
der their commercial use. Several studies [14–29] have
quers, paints, and varnishes; as solvents and stabilizers for
shown excellent naphthalene conversion with high activities;
shoe polishes and floor waxes; as constituents of motor
however, highly selective and stable hydrogenation of
fuels and lubricants; as solvents for pesticides, rubber, as-
naphthalene to tetralin remains challenging to researchers.
Therefore, the development of inexpensive catalysts with
*Corresponding authors (email: csli@home.ipe.ac.cn; sjzhang@home.ipe.ac.cn)

© Science China Press and Springer-Verlag Berlin Heidelberg 2014 chem.scichina.com link.springer.com
 Usman et al. Sci China Chem April (2015) Vol.58 No.4 739

high activity, selectivity, and stability should be developed. samples were kept at a reduced temperature (680 °C) for 3 h
Transition-metal phosphides have recently garnered con- and cooled to room temperature at a nitrogen flow of 100
siderable interest as hydrotreatment catalysts. These materi- cm3/min. Passivation was done at room temperature in a
als possess excellent hydrogen-transfer properties and have 0.99% O2/N2 flow for 3 h to maintain the structure of the
been investigated in hydrodeoxygenation, hydrodenitrifica- catalyst. Other bulk phosphides were prepared via the same
tion, and hydrodesulfurization processes. However, their method but the initial mole ratio of the precursor for Ni2P
function in aromatic hydrogenation has not been sufficiently and Fe2P was set to 1/2 and the reduction temperature was
explored. Understanding the nature of transition-metal pho- maintained at 20 °C higher than the highest reduction tem-
sphides and their application in the hydrogenation of naph- perature. Details of the preparation conditions are listed in
thalene is of great importance. In the present work, we pre- Table 1.
pared and characterized the transition-metal phosphides,
MoP, Ni2P, Co2P, and Fe2P. We investigated these materials 2.3 Catalytic-activity experiment
as a function of naphthalene conversion and chose MoP as a
suitable material for the selective hydrogenation of naph- The hydrogenation reaction of naphthalene over transition
thalene to tetralin. metal phosphides was conducted using a fixed-bed reactor
(i.d.=1 cm) operated at 300 °C and a total pressure of 4 MPa
with 5% naphthalene in n-heptane as a model reactant. The
2 Experimental passivated catalyst was loaded into the isothermal section of
the reactor with glass beads (1 mm diameter) packed at both
2.1 Materials ends of the catalyst. The passivated catalyst was activated in
H2 flowing at 30 L/h and at 450 °C for 2 h. After cooling to
The required chemicals for MoP, Ni2P, Co2P, and Fe2P were the reaction temperature, 5 wt% naphthalene was introduced
provided by Qingdao Wish Chemicals Co., Ltd (China). to the reactor using a 2PB00C (B Satellite Co., China) me-
These chemicals included ammonium heptamolybdate tering pump at 0.5 mL/min into 36 L/h H2 flow and liquid
[(NH4)6Mo7O24·4H2O; (Xilong, 99%)], nickel nitrate hourly space velocity (LHSV) was maintained at 3/h. Liq-
[Ni(NO3)2·6H2O; (Xilong, 99%)], cobalt nitrate [Co(NO3)2· uid products of the reaction were collected in a condenser
6H2O; (Xilong, 99%)], iron nitrate [Fe(NO3)2·9H2O; (Xi- placed at the reactor exit. The reactants and products were
long, 98.5%)], and diammonium phosphate [(NH4)2HPO4; analyzed by GC-MS. Naphthalene conversion is defined in
(Xilong, 99%)]. The chemical used for reactivity tests was Eq. (1).
naphthalene (Sinopharm, >99.5%). The gases used were H2
(Beifen, Grade 5, 99.99%), He (Beifen, Grade 5, 99.99%), M C10 H8 (in)  M C10 H8 (out)
Conversion (mol%) = 100  (1)
CO (Beifen, 99.97%), 0.999% O2/N2 (Beifen, UHP Grade, M C10 H8 (in)
99.99%), O2 (Beifen, UHP Grade, 99.99%), and N2 (Beifen,
Grade 5, 99.99%). Chemical standards for gas chromatog- where M represents molar concentration of inlet and outlet
raphy mass-spectrometry (GC-MS) included naphthalene species. Selectivity was calculated based on the peak areas
and tetralin and were purchased from Sinopharm Co., Ltd of the gas chromatograms, which were obtained by consid-
(China). ering the different sensitivity factors of the GC-MS detector.
The product selectivity for tetralin is defined in Eq. (2).
2.2 Catalysts preparation M C10 H12
Selectivity (mol%) = 100 (2)
All chemicals were used without further purification. Pre- M C10 H8 (in)  M C10 H8 (out)
cursors of the transition-metal phosphides (MoP, Ni2P,
Co2P, and Fe2P) were prepared through wet impregnation The equipment was washed with ethanol and then dried
and temperature-programmed reduction (TPR) as described with nitrogen after each sample run.
in previously published studies [30–32].
Bulk MoP was prepared by adding drops of an aqueous 2.4 Catalyst characterization
solution of (NH4)6Mo7O24·4H2O in deionized water to a
solution of (NH4)2HPO4 in deionized water under stirring. XRD patterns of the passivated catalysts were obtained
The resulting precipitate was stirred while the water was Table 1 Preparation of transition metal phosphides
evaporating to obtain a solid product; this product was dried Metal/Phosphorus Calcination Reduction temp
Bulk phosphides
at 120 °C for 12 h and then calcined at 500 °C for 3 h to (initial mole ratio) temp. (oC) (oC)
obtain the final oxidic precursor. The obtained solid was MoP 1/1 500 680
Ni2P 1/2 500 942
ground to a powder and sieved to 20–40 mesh particles.
Co2P 1/1 500 962
Solid phosphates were reduced to phosphides in a U-shaped
Fe2P 1/2 500 980
quartz reactor with 150 cm3/min of hydrogenous flow. The
740 Usman et al. Sci China Chem April (2015) Vol.58 No.4

using a AXS D8 Focus X-ray diffractometer (Bruker, Ger- XRD patterns of MoP showed major peaks at 2 28.1°,
many) operated at an accelerating voltage of 40 kV and 32.1°, 42.9°, 57.4°, 65.1°, 67.7°, and 74.4°. These patterns
emission current of 40 mA with Ni-filtered Cu K (=0.154 are similar to the standard patterns of MoP described in the
nm) radiation. Angles (2) were measured in steps of JCPDS powder diffraction file, which suggests the complete
0.01°/s between 10° and 80°. The surface areas of the pas- single-phase formation of bulk MoP. The XRD pattern of
sivated samples were obtained using the BET method based Ni2P exhibited four major peaks at 2 40.7°, 44.6°, 47.3°,
on N2 adsorption isotherms obtained at liquid N2 tempera- and 54.1° as well as several peaks with small intensity at 2θ
ture; here, a value of 0.162 nm2 was used for the cross- 54.9°, 66.02°, 72.05°, and 75.01°; these results correspond
sectional area of an N2 molecule. Measurements were per- well with the standard patterns of Ni2P [35]. The three ma-
formed on an ASAP 2020 accelerated surface area. Catalyst jor peaks at 2 40.72°, 40.97°, and 44.07° and the lower-
acidities were determined by NH3-TPD using Auto Chem II intensity peaks at 2=42.05°, 48.7°, 50.3°, 52.65°, and
2920 (Micrometrics, USA) unit equipped with a thermal 56.2° of Co2P were in agreement with the standard Co2P
conductivity detector. In the experiment, 100 mg of the cat- patterns. The XRD patterns of Fe2P were similar to those of
alyst was pretreated in a He flow at 150 °C with a heating Ni2P and showed three major peaks at 2 40.34°, 44.46°,
rate of 10 °C/min for 1 h. The sample was then treated with and 47.2° as well as smaller peaks at 2=52.9°, 54.1°, 54.6°,
a 10% NH3-He flow for 30 min at room temperature and 73.6°, and 79.1°. The Scherrer equation was used to calcu-
then purged in a He flow for 1 h at 100 °C. After the base- late particle sizes from XRD peak areas.
line was stabilized, desorption profiles were measured in a Figure 2 shows SEM analysis of the transition metal
He flow at a heating rate of 10 °C/min to 700 °C. Micro- phosphides. MoP appeared to be regular, smooth, and
scopic observations of the samples were conducted using
SEM with an acceleration voltage of 20 kV in high-vacuum
mode. TEM was performed using a JEM-2100 (JEOL,
USA) system operated at an acceleration voltage of 200 kV.
After samples were prepared through ultrasonic dispersion
in acetone, a drop of the resultant suspension was evapo-
rated onto a holey carbon-supported grid.
To determine the chemical composition of the products,
EDX spectra and maps were obtained from the specimens
using an EDX system coupled to an SEM MLA 250 (FEI
USA) unit. The pyridine-IR spectrum was obtained on a
Nicolet 6700 spectrometer equipped with a cell in situ to
determine the different active sites on the surface of the
transition metal phosphides. Pyridine adsorbed on Lewis
(L-Py) and Brønsted (Py-H+) acid sites exhibited bands at
approximately 1445 to 1460 cm1 and 1540 to 1548 cm1, Figure 1 XRD single phase patterns of transition metal phosphides.
respectively [33,34]. We mixed 10 mg of the passivated
sample with 20 mg of KBr, pressed the mixture into a
self-supporting wafer (30 mg, 13 mm diameter), placed this
wafer into an IR cell, and treated it at 120 °C under vacuum
(0.0013 Pa) for 1 h. After the IR cell had cooled to room
temperature, pyridine vapors were introduced to the cell and
adsorption was conducted for 30 min. Equilibrium was
achieved within 30 min. After vacuuming for 15 min, the
cell was scanned; next measurements were recorded at room
temperature, 100, 150, and 250 °C in vacuum. Pure KBr
was used as a background medium.

3 Results and discussion

3.1 Surface morphology of transition-metal phosphides

XRD patterns were used to determine the phases and phase Figure 2 SEM images of bulk-metal phosphides (a) MoP, (b) Ni2P, (c)
compositions of MoP, Ni2P, Co2P, and Fe2P (Figure 1). The Co2P, (d) Fe2P.
 Usman et al. Sci China Chem April (2015) Vol.58 No.4 741

spongy. Due to the high reduction temperature the crystal- Table 2 Surface area and particle size
linities and particle sizes of Ni2P, Co2P and Fe2P increased BET Particle size (nm)
Sample
(m2/g) Plane (h k l)
and exhibited well-faceted crystal morphologies.
29.4 25.9 25.82 10.91 20.32 9.73 18.20
EDX quantitative analysis and EDX mapping of MoP are MoP 9.6
(001) (100) (101) (110) (111) (102) (201)
shown in Figure 3. Quantitative elemental analysis of the 46.54 41.61 41.43 31.50 32.31 27.52 27.78 22.87
Ni2P 2.3
MoP revealed the atomic percentage of Mo (40%) and P (111) (201) (210) (300) (211) (310) (311) (400)
49.43 43.15 50.60 43.02 44.91 35.89 35.75 36.78 24.81
(40%). This result proved that MoP can be prepared with an Co2P 3.1
(121) (220) (211) (130) (130) (310) (131) (320) (232)
initial mole ratio of 1. The presence of a small percent of 58.14 58.04 52.95 56.52 58.73 38.99 55.12 63.14 53.80
Fe2P 2.6
oxygen is due to the passivation step during transition-metal (110) (101) (111) (201) (210) (002) (300) (211) (302)
phosphide preparation, which helps protect the material
(this is the reason that metal phosphides catalysts require in
situ pre-reduction before an activity test for the activation of
the catalyst). EDX mapping of MoP evaluated the elemental
density and distribution of Mo and P. Comparison of the
EDX maps of the elements with their SEM results proves
that MoP was well prepared, highly homogeneous and rep-
resent atomic mass ratio of 1.

3.2 BET and particle size of transition metal phos-

phides
BET surface areas and particle sizes of all of the metal
phosphides are shown in Table 2. The surface areas of the
bulk transition-metal phosphides were very low except for
MoP. The surface area and particle size were directly relat-
ed to the highest reduction temperature [36]. Lower prepa-
ration temperatures resulted in smaller particle sizes and
larger surface areas. The very high reduction temperatures
of Ni2P, Co2P, and Fe2P produced final products with hard,
faceted shapes and large particle sizes, resulting in smaller
surface areas. Thus, MoP prepared at low reduction temper-
atures showed smaller particle sizes and larger surface areas
than other phosphide materials (Table 2).
The particle size of MoP was in agreement with the XRD
and TEM results (Figure 4). The easy preparation and
physical characteristics of MoP confirm its suitability as an
active material for various hydrotreatment reactions.
Figure 4 TEM analysis of MoP.
3.3 Acidic properties of transition metal phosphides
NH3-TPD was measured to clarify the relationship between
catalyst activity and the number of acidic sites on the cata-
lysts. The strength and type of acidic sites can be identified
from the maximum desorption temperature of ammonia
(Tm) from the catalyst surfaces. The Tm from 50 to 200 °C
corresponds to weak acidic sites; Tm values from 200 to
400 °C corresponds to intermediate acidic sites;, and Tm
values higher than 400 °C corresponds to strong acidic sites
[31]. The NH3-TPD characterization results indicate that all
of the prepared transition metal phosphides have weak,
moderate, and strong acidic sites. Tm values between 80 °C
and 400 °C show weak and moderate acid strengths for all
samples, whereas Tm values between 400 to 700 °C indicate
strong acidic sites over the phosphide catalysts. Figure 5
and Table 3 show that MoP has a total maximum number of

Figure 3 EDX mapping of bulk MoP. Figure 5 NH3-TPD results of transition metal phosphides.
742 Usman et al. Sci China Chem April (2015) Vol.58 No.4

Table 3 Quantitaties of different acid sites of bulk phosphides

Weak acidic sites Moderate acidic sites Strong acidic sites Total acidity
Bulk
material Tmax(oC) Quantity Tmax (oC) Quantity Tmax (oC) Quantity Quantity
(µmol/g) (µmol/g) (µmol/g) (µmol/g)
MoP 84 5.8 277 33.61 402 11.94 51.35
Ni2P 124 2.37 442 5.42 498 3.22 11.01
Co2P 126 0.84 348 6.13 547 6.8 13.77
Fe2P 117 1.24 362 2.55 482 368 7.47

weak and moderate acidic sites are larger compared to Table 4 Pyridine adsorption data for MoP sample at various temperatures
strong acidic sites. Increased numbers of strong acidic sites Pyridine
−1 Quantity (µmol/g)
Temperature (oC) adsorption (cm ) B/L
facilitate cracking, whereas increased numbers of weak and
Peak-B Peak-A B-sites L-sites
moderate acidic sites retard naphthalene cracking and favor
30 1550 1445 2.47 44.73 0.055
its partial hydrogenation. 100 1550 1445 2.47 43.83 0.056
To study the acidity of the phosphides and evaluate the 150 1550 1445 2.44 41.82 0.058
presence of Lewis and Brønsted acidic sites, further MoP 200 1550 1445 2.44 39.28 0.062
was examined by in situ FTIR using pyridine as a probe 250 1550 1445 2.44 38.68 0.063
molecule. Pyridine adsorbed on Lewis acid sites (L-acid)
showed bands at 1447 to 1460 cm1, 1488 to 1503 cm1, demonstrated that more Lewis acid sites are present com-
1580 cm1 and 1600 to 1633 cm1; in contrast, pyridine ad- pared to the Brønsted acid sites.
sorbed on Brønsted acid sites (B-acid) presented as bands at
1485 to 1500 cm1, 1540 cm1, and 1640 cm1 [37]. 3.4 Catalysts test for naphthalene hydrogenation
Figure 6 shows the FTIR spectra of pyridine adsorbed at
MoP; the relevant quantitative data are summarized in Table Naphthalene hydrogenations on the synthesized metal
4. The spectra showed sharp pyridine absorption bands at phosphides (MoP, Ni2P, Co2P, and Fe2P) were analyzed
1450, 1545, and 1650 cm1. Peaks at 1450 cm1 are due to using 5% naphthalene in n-heptane. The passivated phos-
the interaction of pyridine with Lewis acidic sites, whereas phides were activated prior to reaction by H2 streaming (30
peaks at 1545 cm1 are due to the protonation of pyridine L/h) at atmospheric pressure and heating from room tem-
molecules by Brønsted acid sites. The peak at 1650 cm1 is perature to 450 °C at 5 °C/min, followed by holding for 2 h.
due to the vibration of pyridine adsorbed on both the After phosphide activation, the temperature was lowered to
Brønsted and Lewis acidic sites. 300 °C and feeding was commenced. Naphthalene conver-
After thermal treatment of MoP at different reaction sions over the four phosphides were evaluated at 3/h LHSV,
temperatures, the intensity of the spectra for Lewis acid 4 MPa H2, and 300 °C reaction temperature. Activities were
sites decreased but no significant loss in spectra of Brønsted expressed as percent conversion. The reaction pathways for
acidic sites were observed with increasing temperature as naphthalene hydrogenation are shown in Figure 7 [28].
also shown quantitatively in Table 4. The quantitative anal- Figure 8(a) shows the conversion of naphthalene over the
ysis of Brønsted and Lewis acid sites shown in Table 4 metal phosphides during on-stream reaction. The conver-
sion degree of naphthalene was checked after 10 h and ex-
hibited stable conversion until 30 h on stream reaction. The
selectivity of naphthalene toward tetralin over transition-
metal phosphide until 30 h is shown in Figure 8(b), A com-
parative study of naphthalene conversion and tetralin selec-
tivity over the metal phosphides at 10 h is shown in Figure
9.
Among the tested phosphides, bulk MoP showed the
highest activity; this result is attributed to the small crystal
size, large surface area, and acidity of the catalyst. The high
selectivity of naphthalene toward tetralin is due to the

Figure 6 FTIR spectra of MoP after pyridin adsorption. Figure 7 Reaction route of naphthalene hydrogenation.
 Usman et al. Sci China Chem
Figure 8 Graphic distribution of (a) naphthalene conversion and (b) tetralin selectivity over transition metal phosphides.
Figure 9 Catalytic activity of transition-metal phosphides for naphtha-
lene hydrogenation and tetralin selectivity.
presence of large numbers of weak and moderate acidic
sites as well as Lewis acidic sites in the catalyst. Naphtha-
lene hydrogenation occurs in consecutive steps: first, pri-
mary hydrogenation to obtain tetralin; and second, second-
ary hydrogenation to obtain decalin. Complete hydrogena-
tion is caused by an increase in naphthalene and tetralin
adsorption by the active metal or by the direct effect of H+
over Brønsted acid sites [38].
The large crystal sizes, low surface area and acidities of
Ni2P, Co2P, and Fe2P inhibit feed molecules from effective-
ly reacting with metal species, which results in low naph-
thalene conversion. Thus, molecules react on the surface of
the catalysts and yield a primary reaction in the presence of
naphthalene feed with high selectivity toward tetralin. Sec-
ondary hydrogenation and cracking require a sufficient sup-
ply of reactants in the pores of the catalysts, which are re-
tarded by the physical characteristics of the transition-metal
phosphides and thus prevent the occurrence of side reac-
tions and further cracking [39]. MoP showed high conver-
sion and selectivity toward tetralin (>90%) compared to
other products. The hydrogenation of naphthalene to tetralin
occurs on the surface of the active metal such that tetralin
molecules in the naphthalene feed are no longer absorbed
by the catalyst for further hydrogenation. This results in
high selectivity toward tetralin.
April (2015) Vol.58 No.4 743
Another important factor that influence selectivity to-
ward tetralin is the presence of Brønsted and Lewis acid
sites [40,41]. The direct hydrogenation products of naph-
thalene (tetralin and alkyl benzene) can be produced on the
surface of metal phosphides, whereas primary products can
be hydrogenated on the metal/acidic sites of the catalysts.
MoP with acidic sites can absorb reactant molecules and
form carbonium ion intermediates, and then be hydrogenat-
ed by spill-over hydrogen, activated by the metal sites. MoP
with low numbers of strong acid sites produces moderately
activated hydrogen; however, the low numbers of Brønsted
acid sites do not encourage deep protonation of tetralin to
small molecular weight products, which results in high se-
lectivity for tetralin. MoP shows that the maximum amount
of Lewis acid sites, act as electron-deficient centers, where-
as the pi electrons of the aromatic molecule (i.e., naphtha-
lene) tend to be electron donors. Naphthalene molecules can
be absorbed on the surface of Lewis acid sites of MoP with
the formation of pi-complex intermediates, which can be
hydrogenated by activated hydrogen atoms to produce tetra-
lin. However, isomerization is inhibited and no deep crack-
ing products can be formed in this process because of the
weak acidity and electron-deficient centers [38], which re-
sult in high selectivity toward tetralin.
3.5 Effect of temperature
The passivated sample of MoP was loaded into the isother-
mal section of the reactor and activated by a H2 stream (30
L/h) at atmospheric pressure while heating from room tem-
perature to 450 °C at 5 °C/min and then holding for 2 h.
After activation, the temperature was lowered to the desired
temperature, and feeding was introduced. Naphthalene con-
version over MoP catalyst was evaluated at 3/h LHSV,
4 MPa pressure and at 240–360 °C temperature with a
30 °C difference in five continual experiments. The product
sample was obtained after 10 h of reaction on stream and
analyzed via GC-MS. The relevant data are shown in Figure
10. Catalytic activity increased with increasing temperature
and maximum naphthalene conversion achieved at 360 °C.
Such behavior of catalytic activity with the increase in tem-
perature has also seen previously [42,43]. However, tetralin
744 Usman et al. Sci China Chem April (2015) Vol.58 No.4

selectivity decreased after 300 °C. Turnover frequencies at
different reaction temperatures were obtained using the fol-
lowing Eq. (3).
RC
TOF =
QW
where, TOF (1/s), turn over frequency; R (mol/s), reactant
flow rate; C (%), total conversion; Q (mol/g), quantity of
sites; W (g), weight of the catalyst.
The contact time is defined by the following Eq. (4) and
the quantity of acid sites obtained from the NH3-TPD ex-
periment:
QW
 =
F mass transfer effects can be neglected at the conditions em-
where,  (s), contact time; F (mol/s), reactant flow rate.
A summary of TOFs, contact times, and rates of reaction
at different reaction temperatures is provided in Table 5.
The rates of reaction and conversion increased with tem-
perature. At low reaction temperature, the product formed in
the highest yield was tetralin. Tetralin production decreased
slightly after 300 °C and a corresponding growth in decalin
and alkyl benzene concentrations was observed. These re-
sults indicate that maximum naphthalene conversion to te-
tralin required a specific reaction temperature. According to
our experiments, 300 °C is the optimal temperature for the
selective hydrogenation of naphthalene to tetralin.
Mass-transport and heat-transfer calculations [44] were
implemented based on reactivity tests at different reaction
temperatures, 4 MPa pressure, and 5% naphthalene feed
over MoP in the fixed-bed reactor. The Weisz-Prater crite-
rion CWP for internal diffusion was calculated for the dif-
ferent rates of reaction at a contact time of 123.6 s.
(3)

 rA(obs) c R 2
If CWP   1, internal mass-transfer ef-
De CAs
fects can be neglected. The units and physical meaning of
each parameter used for the criterion are listed in Table 6.

Observed rates rA(obs) were calculated based on the tem-
perature and conversion. The corresponding CWP at different
reaction rates are listed in Table 7. The highest Weisz-Prater
criterion CWP was 0.014  1, which indicates that internal
(4)
ployed for the kinetics study in the present work. Similarly,
rA  b Rn
for Mears criterion, if  0.15, external mass-
kc CAb
transfer effects can be neglected. The units and physical
meaning of each parameter used for the criterion are listed
in Table 8, and the corresponding Mears value at different
reaction rates are listed in Table 7.
The highest Mears criterion (CM) was 0.0028  0.15,
which indicates that internal mass transfer effects can be
neglected at the conditions employed for the kinetics study
of the hydrogenation reaction of naphthalene over MoP.
3.6 Stability test of bulk molybdenum phosphide

Based on comparative study on transition metal phosphides,

MoP exhibited excellent activity and high selectivity toward
Table 6 Parameters in the Weisz-Prater Criterion
Parameter Description Value
R Catalyst particle radius (cm) 0.065
c Solid catalyst density (g cm3) 0.561
CAs (473K) Gas concentration at the catalyst surface (mol cm3) 6.8×103
De Effective diffusivity (cm2 s1) 0.002

Table 7 The observed reaction rates and corresponding Mears and

Weisz-Prater criterion
T (K) 
rA(obs) (mol g1 s1) CM CWP
Figure 10 Effect of temperature on the activity and selectivity of MoP 513 1.68×105 8.0×104 2.9×103
for naphthalene hydrogenation and tetralin selectivity. 543 3.48×105 1.6×103 6.0×103
573 4.94×105 2.3×103 7.0×102
Table 5 Rate of reaction and turn over frequency at different reaction 603 5.06×105 2.4×103 8.8×103
temperatures over MoP 633 6.0×105 2.8×103 1.04×102
T a) FR b) C c) W d) S e) CT f) R g) TOF h)
5
240 2.33 32 5.61 51.35 123.6 1.68 × 10 0.00242 Table 8 Parameters in the Mears criterion
270 2.33 60 5.61 51.35 123.6 3.48 × 105 0.00501 Parameter Description Value
300 2.33 88 5.61 51.35 123.6 4.94 × 105 0.00711 n reaction order 1
330 2.33 90 5.61 51.35 123.6 5.06 × 105 0.00727 R catalyst particle radius (cm) 0.065
360 2.33 97 5.61 51.35 123.6 6.0 × 105 0.00784 ρb bulk density of catalyst bed (g cm−3) 0.561
a) Reaction temperature (oC); b) Reactant flow rate (µmol/s); c) Naph- kc mass transfer coefficient (cm s−1) 0.112
thalene conversion (mol%); d) Catalyst weight (g); e) acid sites (µmol/g);
CAb bulk gas concentration of (mol cm−3) 6.8×103
f) Contact time; g) Rate of reaction (mol/g s); h) TOF (s1)
 Usman et al. Sci China Chem
Figure 11 Activity and stability of MoP for 100 h on-stream reaction.
tetralin. In addition the catalytic stability test on MoP was
performed in a continuous fixed-bed reactor at optimum
reaction conditions: 3/h LHSV, 4 MPa of H2, and 300 °C
reaction temperature for 100 h (Figure 11). The catalytic
activity revealed a high naphthalene conversion (~94%) and
tetralin selectivity (~90%) for 100 h on-stream reaction. The
high stability observed is attributed to the presence of weak
and moderate acidic sites and the low ratio of Brønsted to
Lewis acid sites, thereby confirming MoP as a highly stable
material for naphthalene hydrogenation to tetralin. The high
stability and selectivity of MoP compared to the known
literature [14–29] in the fixed-bed reactor at the reaction
conditions employed in the present work qualify the materi-
al as a promising one for tetralin industrialization.
4 Conclusions
Hydrogenation of naphthalene in heptane was conducted
over transition-metal phosphides MoP, Ni2P, Co2P, and
Fe2P. Among all the transition metal phosphides tested,
MoP with small particle sizes and large surface areas could
be prepared at low reduction temperatures. High concentra-
tion of moderate acidic strength and low ratio of Brønsted to
Lewis acidic sites indicates MoP as a novel approach for the
high-selective production of tetralin from naphthalene. The
most suitable temperature for naphthalene to tetralin hydro-
genation over MoP was 300 °C. Weisz-Prater and Mears
criterion analyses revealed no heat or mass transfer limita-
tions under the conditions applied in the present work. The
stability of MoP in the fixed-bed reactor over 100 h on-
stream reaction showed high naphthalene conversion
(~ 94%) and tetralin selectivity (~ 90%), which indicate that
this material is a promising one. However, exploring appro-
priate support materials for MoP is necessary to lower cata-
lyst costs for tetralin industrialization and also promotes the
applications of this material in the selective hydrogenation
of other aromatics.
April (2015) Vol.58 No.4 745
We are grateful for financial support from the Special Funds of the Na-
tional Natural Science Foundation of China (21127011), National High
Technology Research and Development Program of China
(2011AA050606) and National Natural Science Foundation of China
(Petrochemical Joint Fund, U1162106)
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