30

Chinese Journal of Catalysis

Vol. 30 No. 7
: 0253-9837(2009)07-0606-07

2009 7
July 2009
: 606~612

, ,

, ,

, , , 300071
, 2,5- 2,5-
. X .
, , . ,
2,5-, ,
, 2,5- 2,5-. 5
.
; ; 2,5-;
O643

Hydrogenation of Nitro Compounds Catalyzed by Urushibara Nickel Catalysts

LIU Hao, LI Ruoyu, ZHANG Meng, LI Wei*, ZHANG Minghui, TAO Keyi
Tianjin Key Laboratory of Energy Material Chemistry, Engineering Research Center of Energy Storage and Conversion of Ministry of
Education, College of Chemistry, Nankai University, Tianjin 300071, China
Abstract: The Urushibara nickel catalysts were prepared by reducing nickel chloride with Zn powder. The structure and composition of the
catalysts were characterized by X-ray diffraction, inductively coupled plasma analysis, and transmission electron microscopy. The optimal
preparation conditions of the catalysts were determined. The Urushibara nickel catalysts were applied to the selective hydrogenation of
m-dinitrobenzene to m-phenylenediamine and 2,5-dichloronitrobenzene to 2,5-dichloroaniline. The effects of Zn powder, developing agent,
temperature of catalyst preparation and reaction conditions such as solvent and pressure on the catalyst activity were studied. The Urushibara
nickel catalysts exhibited high catalytic activity and selectivity for m-phenylenediamine and 2,5-dichloroaniline. The optimized content of
water in solvent remarkably promoted the reaction. An appropriate quantity of the dechlorination inhibitor in the hydrogenation of
2,5-dichloronitrobenzene evidently increased the reaction rate and the selectivity for 2,5-dichloroaniline. The catalysts could be reused five
times without any significant loss in their catalytic activity.
Key words: Urushibara nickel; m-dinitrobenzene; 2,5-dichloronitrobenzene; hydrogenation

[1]

, .

1952 [11] Zn

(, ppt-Ni)

[2~4]

, ,

[12~15].

[5~9]

[10]

: 2009-01-06.
:

. Tel/Fax: (022)235086621; E-mail: weili@nankai.edu.cn

607

, , [16],

1.3

100 ml (

.
(MDNB)

) ,

(MPD) 2,5- (2,5-

, H2

DCNB) 2,5- (2,5-DCAN) ,

, H2 ,

0 , , 800

r/min,

1
1.1

. GC-9790

(), OV-101

12.6 g (

(0.25 mm 30 m), FID .

, ) 4 ml ,
, , 10 ml NiCl26H2O (

, ) (

2.1

0.25 g/ml) , ,

2.1.1

. ,

, ,

. , U-Ni-A ,

(ppt-Ni) , ,

99.8%, 99.9%,

, . 180 ml 20%

U-Ni-B U-Ni-A 6 ,

() U-Ni-A,

99.1%

160 ml 10% NaOH ()

99.8%. U-Ni-A U-Ni-B 2,5-

U-Ni-B.

2,5- 2,5-

1.2

, U-Ni-B ,

Rigaku D/

. , U-Ni-A U-Ni-B .

max-2500 X (XRD), Cu K ( =

1 XRD .

0.154 05 nm). Philips Tacnai F20

, ppt-Ni

(TEM) , 200 kV.

(ZnCl24Zn(OH)2H2O) ,

IRIS Intrepid (ICP)

U-Ni-B ,

U-Ni-A , .
1

Table 1 Influence of the developing agent on catalytic performance of the Urushibara nickel catalysts (U-Ni) for hydrogenation of nitro
compounds
MDNB hydrogenationb
Catalysta

2,5-DCNB hydrogenationc

Catalyst

Reaction

Conversion of

Selectivity for

Catalyst

Reaction

Conversion of

Selectivity for

amount (g)

time (min)

MDNB (%)

MPD (%)

amount (g)

time (min)

2,5-DCNB (%)

2,5-DCAN (%)

U-Ni-A

0.2

34

99.8

99.9

0.4

55

U-Ni-B

1.2

220

99.1

99.8

1.1

100

100
99.0

93.8
93.1

U-Ni-A and U-Ni-B were obtained by treatment of ppt-Ni (prepared by reducing nickel chloride with Zn powder) with acetic acid and NaOH
solution, respectively.
b
Other conditions: 4 g MDNB , 50 ml ethanol, 2.5 MPa H2, 80 oC, 800 r/min.
c
Other conditions: 8 g 2,5-DCNB , 48 ml ethanol, 1.5 MPa H2, 85 oC, 800 r/min.
MDNBm-dinitrobenzene; MPDm-phenylenediamine; 2,5-DCNB2,5-dichloronitrobenzene; 2,5-DCAN2,5-dichloroaniline.

608

Intensity

(1)

NaOH U-Ni-B
, ZnCl2 2NaOH = Zn(OH)2

(2)

2NaCl, Zn(OH)2 2NaOH = Na2ZnO2 2H2O,

ZnCl2 4NaOH = Na2ZnO2 2NaCl

2H2O. , Zn2NaOH = Na2ZnO2 H2, ZnO

2NaOH = Na2ZnO2 H2O, Na2ZnO2 ,

Zn(OH)2 , Zn(OH)2 NaOH

(3)
10

Na2ZnO2, Zn(OH)2
20

30

, [17]. 1 ,

ZnCl24Zn(OH)2H2O

ZnO
Zn
Ni

30

40
50
o
2/( )

60

70

80

ppt-Ni, U-Ni-A U-Ni-B XRD

Fig. 1. XRD patterns of different samples. (1) ppt-Ni; (2) U-Ni-A; (3)
U-Ni-B.

NaOH , U-Ni-B
, . ,
,
, .
, U-Ni-B

JCPDS 3-1051, 2 = 44.87, 52.30 76.93

, U-Ni-B U-Ni-A (

, , ppt-Ni U-Ni-B

1). NaOH 20%,

. ppt-Ni

, 10%

. U-Ni-A ,

NaOH 50%~70%[16].

U-Ni-A .

, .

2 U-Ni-A U-Ni-B TEM .

180 ml 20% U-Ni-A

, U-Ni-A 150~200 nm

Ni:Zn 3:1. Zn Ni

, 4 nm

, , Ni

; U-Ni-B .

, Al [18].

, U-Ni-A U-Ni-B .

2.1.2

,
[16]

180 ml 20% ,

. NiCl2 + 2Zn Ni-Zn + ZnCl2,

U-Ni-A

Zn + H2O ZnO + H2 ZnCl2 + 4ZnO + 5H2O

2.

ZnCl24Zn(OH)2H2O ,

99% , 2,5-

, ,

2,5-

[16]

[17]

, ,

100% 93%~94%,

.
2

U-Ni-A

Table 2 Influence of catalyst preparation temperature on

performance of U-Ni-A catalyst
Preparation
o

temperature ( C)

U-Ni-A U-Ni-B TEM

Fig. 2. TEM images of U-Ni-A (a) and U-Ni-B (b) samples.

Reaction time for 100% conversion (min)

MDNB hydrogenationa 2,5-DCNB ydrogenationb

30

84

91

45

71

67

60

66

55

80

65

51

Reaction conditions: 0.2 g catalyst, 4 g MDNB, 50 ml ethanol, 1.0

MPa H2, 80 oC, 800 r/min.
b
Reaction conditions: 0.4 g catalyst, 8 g 2,5-DCNB , 48 ml ethanol, 1.5
MPa H2, 85 oC, 800 r/min.

609

. 2 , 60 80 oC
o

20% 25% , XRD

(30 C)

4. , , 20%

60 o C , 180 ml 20%

. ,

, ,
; ,
Intensity

, , ,
,
, .

(1)
(2)

3 U-Ni-A XRD
. , 30 oC ,

10

20

30

ZnO, 45 C U-Ni-A ZnO

, 60 oC U-Ni-A ZnO ,
, ,

40
50
2/( )

60

70

80

U-Ni-A XRD

Fig. 4. XRD patterns of U-Ni-A samples developed by acetic acid with

different concentrations. (1) 20%; (2) 25%.

,
60 oC.

2.1.3

60 o C U-Ni-A

Zn
Zn .

U-Ni-A
3. ,

Ni

ZnO

.
,

Intensity

(1)

(2)

[19].

,
. ,

(3)

.
10

20

30

40

50

60

70

80

2.2

2/( )

2.2.1

U-Ni-A XRD

Fig. 3. XRD patterns of U-Ni-A samples prepared at 30 oC (1), 45

o
C (2), and 60 oC (3).

4 .

U-Ni-A

Table 3 Effect of the pellet size of zinc particles on catalytic activity of U-Ni-A
Zn particle
(mesh)

MDNB hydrogenationa

2,5-DCNB hydrogenationb

Reaction time

Conversion of

Selectivity for

Reaction time

Conversion of

Selectivity for

(min)

MDNB (%)

MPD (%)

(min)

2,5-DCNB (%)

2,5-DCAN (%)

Industrial grade

64

97.3

99.5

193

99.5

92.7

200300

50

97.8

99.8

164

99.8

93.1

800

34

99.8

99.9

105

Reaction conditions: 0.2 g U-Ni-A, 4 g MDNB , 50 ml ethanol, 2.5 MPa H2, 80 oC, 800 r/min.
b
Reaction conditions: 0.4 g U-Ni-A, 8 g 2,5-DCNB , 48 ml ethanol, 0.8 MPa H2, 85 oC, 800 r/min.

100

93.3

610

30

Table 4 Influence of H2 pressure on the hydrogenation of nitro compounds

MDNB hydrogenationa

2,5-DCNB hydrogenationb

H2 pressure

Reaction time

Conversion of

Selectivity for

H2 pressure

Reaction time

Conversion of

Selectivity for

(MPa)

(min)

MDNB (%)

MPD (%)

(MPa)

(min)

2,5-DCNB (%)

2,5-DCAN (%)

2.5

34

99.8

99.9

1.5

55

100

93.3

1.0

66

99.2

99.8

0.8

105

100

93.8

Reaction conditions: 0.2 g U-Ni-A, 4 g MDNB, 50 ml ethanol, 80 oC, 800 r/min.

b
Reaction conditions: 0.4 g U-Ni-A, 8 g 2,5-DCNB, 48 ml ethanol, 85 oC, 800 r/min.

, , .

2.2.3

2.2.2

TEM ( 2(a)) ,

[20]

. 2,5-

, . Ni/SiO2

, CCl C , 2,5-

25 , 65.6% 95%.

2,5-

[21], ,

, 5.

. [3],

Ning

(0.078 g/100 g H2O, 20

C), 2,5-,

6. , 0.2% ,

. 5 ,

93.1% 99.6%.

, 4% 8% ,

0.4% , 99.7%,

, ; 2,5-

, 12% ,

HCl
, [3], ,

, 4% .
,

, . 0.2%

, ,

; , ,

2.3

[20]

. ,
5

7. ,

Table 5 Influence of the mixed solvent of water and ethanol on the hydrogenation of nitro compounds

2,5-DCNB hydrogenationb

MDNB hydrogenationa

Volume percent of
water in solvent

Reaction time

Conversion of

Selectivity for

Reaction time

Conversion of

Selectivity for

(%)

(min)

MDNB (%)

MPD (%)

(min)

2,5-DCNB (%)

2,5-DCAN (%)

66

99.2

99.8

105

100

93.1

40

100

99.9

42

100

95.9

39

100

99.8

49

100

96.6

12

57

100

99.5

51

100

96.0

Reaction conditions: 0.2 g U-Ni-A, 4 g MDNB, 50 ml solvent, 1.0 MPa H2, 80 oC, 800 r/min.
b
Reaction conditions: 0.4 g U-Ni-A, 8 g 2,5-DCNB, 48 ml solvent, 0.8 MPa H2, 85 oC, 800 r/min.

611

[22] Ni-Pt

2,5-

Table 6 Influence of the dicyandiamide content on the hydrogenation of 2,5-DCNB

, 4 ,
99.2%, 5 ,

Content of

Conversion of

Selectivity for

dicyandiamide (%)

2,5-DCNB (%)

2,5-DCAN (%)

100

93.1

Ru-Pt/-Al2O3 2,5-

0.2

100

99.6

, , 2,5-

0.4

100

99.7

100%, 2,5- 77.6%,

99.6%. [9]

Reaction conditions: 0.4 g U-Ni-A, 8 g 2,5-DCNB, 48 ml ethanol, 0.8

MPa H2, 85 oC, 800 r/min.

4 h, 99.3%,
. 5 , 2,5-

5 ,

100%, 2,5-

99%, 2,5-

99.8%,

2,5- 100%. Telkar

, .

U-Ni-A

Table 7 Stability of U-Ni-A catalyst for catalytic hydrogenation

MDNB hydrogenationa
Recycle

2,5-DCNB hydrogenationb

Reaction time

Conversion of

Selectivity for

Reaction time

Conversion of

Selectivity for

(min)

MDNB (%)

MPD (%)

(min)

2,5-DCNB (%)

2,5-DCAN (%)

66

100

99.9

105

100

99.7

80

100

99.8

120

100

99.8

80

100

99.8

120

100

99.8

80

99.8

99.8

120

100

99.8

80

99.6

99.6

120

100

99.8

Reaction conditions: 0.2 g U-Ni-A, 4 g MDNB, 46 ml ethanol + 4 ml H2O, 1.0 MPa H2, 80 C, 800 r/min.
Reaction conditions: 0.4 g U-Ni-A, 8 g 2,5-DCNB, 0.016 g C2H4N4, 46 ml ethanol + 2 ml H2O, 0.8 MPa H2, 85 oC, 800 r/min.

30

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Chen L. Dyes Ind), 2002, 39(2): 32

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5 , ,
, , , .

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Shamir N, Mintz M H. J Catal, 1986, 101: 28

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30

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2008 (JCR)
(Thomson Reuters) 2008 (Journal Citation Reports, JCR),
.

Total Cites

Impact Factor

5-Year Impact Factor

Immediacy Index

Articles

Cited Half-life

934

0.707

0.662

0.105

228

3.8

()