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Highly Selective and Stable Hydrogenation of Heavy Aromatic-Naphthalene Over Transition Metal Phosphides
Highly Selective and Stable Hydrogenation of Heavy Aromatic-Naphthalene Over Transition Metal Phosphides
Highly Selective and Stable Hydrogenation of Heavy Aromatic-Naphthalene Over Transition Metal Phosphides
Chemistry
• ARTICLES • April 2015 Vol.58 No.4: 738–746
doi: 10.1007/s11426-014-5199-3
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.
© 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 cm1 and 1540 to 1548 cm1, 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.
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.
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
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 cm1, 1488 to 1503 cm1, demonstrated that more Lewis acid sites are present com-
1580 cm1 and 1600 to 1633 cm1; in contrast, pyridine ad- pared to the Brønsted acid sites.
sorbed on Brønsted acid sites (B-acid) presented as bands at
1485 to 1500 cm1, 1540 cm1, and 1640 cm1 [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 cm1. Peaks at 1450 cm1 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 cm1 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 cm1 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 April (2015) Vol.58 No.4 743
Figure 8 Graphic distribution of (a) naphthalene conversion and (b) tetralin selectivity over transition metal phosphides.
selectivity decreased after 300 °C. Turnover frequencies at implemented based on reactivity tests at different reaction
different reaction temperatures were obtained using the fol- temperatures, 4 MPa pressure, and 5% naphthalene feed
lowing Eq. (3). over MoP in the fixed-bed reactor. The Weisz-Prater crite-
rion CWP for internal diffusion was calculated for the dif-
RC ferent rates of reaction at a contact time of 123.6 s.
TOF = (3)
QW
rA(obs) c R 2
If CWP 1, internal mass-transfer ef-
where, TOF (1/s), turn over frequency; R (mol/s), reactant De CAs
flow rate; C (%), total conversion; Q (mol/g), quantity of fects can be neglected. The units and physical meaning of
sites; W (g), weight of the catalyst. each parameter used for the criterion are listed in Table 6.
The contact time is defined by the following Eq. (4) and
Observed rates rA(obs) were calculated based on the tem-
the quantity of acid sites obtained from the NH3-TPD ex-
periment: perature and conversion. The corresponding CWP at different
reaction rates are listed in Table 7. The highest Weisz-Prater
QW criterion CWP was 0.014 1, which indicates that internal
= (4)
F mass transfer effects can be neglected at the conditions em-
ployed for the kinetics study in the present work. Similarly,
where, (s), contact time; F (mol/s), reactant flow rate.
A summary of TOFs, contact times, and rates of reaction rA b Rn
for Mears criterion, if 0.15, external mass-
at different reaction temperatures is provided in Table 5. kc CAb
The rates of reaction and conversion increased with tem- transfer effects can be neglected. The units and physical
perature. At low reaction temperature, the product formed in meaning of each parameter used for the criterion are listed
the highest yield was tetralin. Tetralin production decreased in Table 8, and the corresponding Mears value at different
slightly after 300 °C and a corresponding growth in decalin reaction rates are listed in Table 7.
and alkyl benzene concentrations was observed. These re- The highest Mears criterion (CM) was 0.0028 0.15,
sults indicate that maximum naphthalene conversion to te- which indicates that internal mass transfer effects can be
tralin required a specific reaction temperature. According to neglected at the conditions employed for the kinetics study
our experiments, 300 °C is the optimal temperature for the of the hydrogenation reaction of naphthalene over MoP.
selective hydrogenation of naphthalene to tetralin.
Mass-transport and heat-transfer calculations [44] were
3.6 Stability test of bulk molybdenum phosphide
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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