Journal of the Japan Petroleum Institute, 47, (2), 115120 (2004)

115

[Regular Paper]

Effect of Addition Method of Phosphorus on Alumina-supported NiMoP

Catalysts Hydrodesulfurization of 4,6-Dimethyldibenzothiophene
and Characterization Using MAS NMR
Hideki GODO1)*, Kazuhiko HAGIWARA1), Takayuki OSAKI1),
Takashi FUJIKAWA1), and Eika W. QIAN2)
1)

Research & Development Center, Cosmo Oil Co., Ltd., 1134-2 Gongendo, Satte, Saitama 340-0193, JAPAN
2)
Dept. of Chemical Engineering, Tokyo University of Agriculture & Technology,
2-24-16 Naka-machi, Koganei, Tokyo 184-8588, JAPAN
(Received July 3, 2003)

A series of Ni_Mo_P/Al2O3 catalysts with phosphorus added by different methods were prepared. The
hydrodesulfurization of 4,6-dimethyldibenzothiophene (4,6-DMDBT) was carried out using the catalysts. The
catalysts were also characterized using magic angle spinning nuclear magnetic resonance (MAS NMR).
The hydrodesulfurization activities of phosphorized catalysts were changed from that of NiMo/Al2O3 catalyst.
Furthermore, the method for phosphorus addition affected their hydrodesulfurization activities. However, the
activation energy and product selectivity for the hydrodesulfurization of 4,6-DMDBT were almost the same for
all catalysts. It was indicated that the phosphorus content and the addition method did not change the mechanism of hydrodesulfurization of 4,6-DMDBT.
MAS NMR showed that the phosphorus addition method affected the dispersion of phosphorus on alumina.
Catalyst with higher dispersion of phosphorus on alumina showed higher activity for hydrodesulfurization.
Phosphorus addition may affect the structure of the molybdenum cluster and the degree of sulfidation of active
metal.

Keywords
Nickel molybdenum catalyst, Phosphorus addition, Hydrodesulfurization, Dimethyldibenzothiophene,
Magic angle spinning NMR, Phosphorus dispersion

1.

Mo

Prins 14) P

1)

CoMo

NiMo

CoMo P

BTDBT

Mo Ni(Co) 3

2)14) P

NMR P

NiMo

P S

P 4,6-

4,6-DMDBT

6)10)

Gishti 11) P

Zeuthen 12) P
* To whom correspondence should be addressed.
* E-mail: hideki_godo@cosmo-oil.co.jp
J. Jpn. Petrol. Inst.,

P NiMoP 4,6DMDBT
Vol. 47,

No. 2, 2004

116
P

Table 1

MAS magic angle spinning NMR nuclear magnetic reso-

Composition and Surface Area of Catalysts

nanceP Al

Catalyst

NiO
[mass]

MoO3
[mass]

P2O5
[mass]

Surface area
[m2/g]

P P

Cat.A
Cat.B
Cat.C
Cat.D
Cat.E

4.1
4.1
4.1
3.9
3.9

16.5
16.5
16.5
16.5
16.5

0
3.0
3.0
2.7
2.7

268
237
226
229
236

2.

2. 1.

NiMo/Al2O3 NiO: 4 massMoO3: 16 mass

P 4 NiMoP/Al2O3 NiO: 4 mass

MoO3: 16 massP2O5: 3 mass

2. 4.

-Al2O3: : 318 m2/g

MoNi P

RX-610SA4,6-DMDBT HDS

kHDS

Eqs.1
2

1Mo_Ni/Al2O3Cat.A

HDS = (1 Sproduct / Sfeed) 100

k = ln(Sfeed / Sproduct) WHSV

-Al2O3 Mo 500 Mo/

Al2O3 Mo/Al2O3 Ni
500

Mo_Ni/Al

2O3

Sfeed:

Sproduct:

2NiMoP/Al2O3Cat.B

GC-

Ni Mo P

AED GC gas chromatography: Hewlett Packard 5890 AED

70 NiMoP atomic emission detector: Hewlett Packard 5921A

NiMoP -Al2O3 500

Eq.3

NiMoP/Al2O3

3P_Mo_Ni/Al2O3Cat.C

100

-Al2O3 P 500 P/Al2O3

MAS NMR

2. 5.

P/Al2O3 Mo 500

JNM-CMX-400

P_Mo/Al2O3 P_Mo/Al2O3

31P-MAS NMR

Ni 500 P_Mo_Ni/Al2O3

/4 15 sMAS 12 kHz

600 31P 2

4Mo_P_Ni/Al2O3Cat.D

(NH4)2HPO4 H3PO4 1.3

Cat.C 1 Mo 2 P
3 Ni Mo_P_Ni/Al2O3
5Mo_Ni_P/Al2O3Cat.E

/12 2 sMAS 12 kHz 400

27

Al 1 mol/l Al(NO3)3

Cat.C 1 Mo 2 Ni
3 P Mo_Ni_P/Al2O3
2. 2.

ppm 27Al-MAS NMR

ICPS-2200

3.
3. 1.

Table 1

Cat.A P

28BET

P Cat.A

P2O5 3 mass

2. 3.

30 m2/g

350 1 H2S(5 vol)/H2

3. 2.

4,6-DMDBT Table 2
P Cat.AP Mo

0.4 mass 4,6-DMDBTAldrich Chem. Co.

NiCat.DCat.E

P Cat.C P

: 230270: 4.9 MPaWHSV:

10 h1: 700 m3(normal)/kl

Cat.BP

1.2

Cat.B > Cat.C > Cat.A > Cat.D > Cat.E

J. Jpn. Petrol. Inst.,

Vol. 47,

No. 2, 2004

117
Table 2

Hydrodesulfurization of 4,6-DMDBT

Table 3
1

Activation Energy

Catalyst

Temperature []

HDS []

kHDS [h ]

Catalyst

Activation energy [kJ/mol]

Cat.A

230
250
270
230
250
270
230
250
270
230
250
270
230
250
270

19.7
51.0
78.8
26.0
58.0
87.5
23.5
55.3
83.2
21.0
47.0
76.1
19.7
41.0
69.2

2.2
7.0
16.2
2.7
8.5
21.4
2.5
8.1
18.3
2.3
6.3
15.1
2.1
5.4
12.8

Cat.A
Cat.B
Cat.C
Cat.D
Cat.E

133
137
132
125
122

Cat.B

Cat.C

Cat.D

Cat.E

Fig. 2

Hydrodesulfurization Pathway for 4,6-DMDBT

DMCHB 3,3-
3,3-DMBCH
Figs. 37
3,3DMCHB 3,3-DMBP 3,3-DMBCH
Fig. 1

Mochida 16),17)

Arrhenius Plots of kHDS

DBT C_S
BP
4,6-DMDBT

NiMo P

C_S

Table 2 Fig. 1

4,6-DMDBT

4,6-

DMDBT C_S 3,3-DMBP

Table 3

3,3-DMCHB

130 8 kJ/mol31 2 kcal/molZhang CoMo/

3,3-DMBCH

Al2O3 33 2 kcal/mol

3,3-DMCHB

15)

NiMo 4,6-

NiMo 4,6-DMDBT

DMDBT P P

P P

3. 3.

Kabe 1) 4,6-DMDBT

P P

GC-AED

4,6-DMDBT Fig. 2

3,3-3,3-

NiMo P P

DMBP 3,3-

3,3-DMCHB 3,3-

J. Jpn. Petrol. Inst.,

Vol. 47,

No. 2, 2004

118

Fig. 3 Effect of Temperature on Selectivity in Hydrodesulfurization

of 4,6-DMDBT for Cat.A

Fig. 6 Effect of Temperature on Selectivity in Hydrodesulfurization

of 4,6-DMDBT for Cat.D

Fig. 4 Effect of Temperature on Selectivity in Hydrodesulfurization

of 4,6-DMDBT for Cat.B

Fig. 7 Effect of Temperature on Selectivity in Hydrodesulfurization

of 4,6-DMDBT for Cat.E

Fig. 5 Effect of Temperature on Selectivity in Hydrodesulfurization

of 4,6-DMDBT for Cat.C
Fig. 8

31

P-MAS NMR Spectra of Catalysts with Added

Phosphorus

3. 4.

31

18)

P-MAS NMR
31

Fig. 8 P P-MAS NMR

Ni

Cat.B

P Ni

15 ppm P

J. Jpn. Petrol. Inst.,

Vol. 47,

No. 2, 2004

119
22)AlPO4 40 ppm 19)
P
-Al2O3
4 Al 6 Al
AlPO4
-Al2O3 Al P

AlPO4 P
3 mass
AlPO4

31

P-MAS NMR

Fig. 8 AlPO4 30 ppm

Fig. 9

27

Al-MAS NMR Spectra of Catalysts

4.

NiMo P
21 ppm 6 ppm

4 NiMoP 4,6-DMDBT

P monomeric polymeric P

MAS NMR PAl

31

1 Cat.B > Cat.C > Cat.A > Cat.D > Cat.E

19),20)Cat.B P

NiMo P

P
P P
P

2 4,6-DMDBT
130 8 kJ/mol
3 4,6-DMDBT
3,3-DMCHB

3,3-DMBP

P Cat.B > Cat.CCat.D > Cat.E

3,3-DMBCH

4,6-DMDBT Cat.B > Cat.C > Cat.D >

Cat.E P

NiMo P P

Decanio 19)

4,6-DMDBT

NMR IR Mo

P P monomeric

Mo

5MAS NMR Al P

Mo

P P P

Ni_Mo_S

19) Mo

P Cat.B > Cat.CCat.D > Cat.E

Mo

21)Cat.B

P Mo

6NiMo P

P AlPO4 P

30 ppm

References

P AlPO4

3. 5.

27

Al-MAS NMR

Fig. 9 27Al-MAS NMR

-Al2O3 27Al-MAS NMR 6 ppm 6 Al
66 ppm 4 Al
J. Jpn. Petrol. Inst.,

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NiMoP P
4,6- NMR
1)1)1)1)2)
1)

340-0193 1134-2

2)

184-8588 2-24-16

NiMo P

NiMo P P 4,6-DMDBT

4 NiMoP 4,6-

4,6-DMDBT MAS NMR

MAS NMR

NiMoP P

P P

Mo

J. Jpn. Petrol. Inst.,

Vol. 47,

No. 2, 2004