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CATALEYDSIS
A: GENERAL
ELSEVIER
Wang, Ming-Hua
Abstract
An amorphous NiB/SiO2 catalyst, with a large specific surface area, was prepared by a reductive-impregnation method. The
selective hydrogenation of cyclopentadiene to cyclopentene was carried out in a continuous flow fix-bed reactor at
atmospheric pressure and with 10 g g cat -I h -l of cyclopentadiene feed. The catalyst showed high selectivity and stability.
Cyclopentene was obtained in 96--100% yield at complete conversion of cyclopentadiene at temperatures ranging from 80C
to 200C and no significant decrease of the activity was observed during the reaction period of 500 h. The catalyst sample was
characterized by ICP, XRD, DSC, SEM, XPS, BET and 02 adsorption. XRD measurement revealed that the amorphous state
was kept after catalytic reaction. Differential kinetic study showed that the hydrogenation proceeded according to a RidealEley mechanism. 1997 Elsevier Science B.V.
Keywords: Supported amorphous alloy; Nickel-boron alloy; Cyclopentadiene hydrogenation; Catalytic activity; Differential
kinetics
1. Introduction
solid phase reaction conditions used widely in industry. For most hydrogenation catalysts such as Pd, Pt,
Ni, Cu [7-10], at the low ratio of PH2/PD(Po: the
pressure of cyclopentadiene), cyclopentene is produced with 100% selectivity at low conversion of
cyclopentadiene, whereas the increase in P~:/Po or
W/Fo decreases the selectivity. The unconverted
cyclopentadiene at low conversion is easily polymerized on catalysts at the reaction temperature, which
leads to the deactivation of the catalysts and also to
low yields of cyclopentene. These phenomena are
commercially impracticable. For these reasons, it is
a crucial subject to prepare special catalysts in order to
obtain cyclopentene at nearly 100% selectivity at
complete conversion of cyclopentadiene.
102
2. Experimental
2.1. Materials
All chemicals employed were of reagent grade and
were used without further purification.
(1)
(2)
103
"- ~
100
I00
90.0
90.0
80.0
80 0
..~
8
~2
70.0
70.0
20
40
60
80
100
120
140
160
I80 2 0 0
Feed-rate(ml.min"t)
Fig. 1. Effect of N2 feed-rate on CPD conversion and CPE selectivity (CPD feed=10 g cat-t h , H2 : CPD=I.4, temperature
120C).
104
O ~ O O O O O
q
r.,,i
I00
100
90.0
90.0
80.0
80.0
II
G~
g g g g g g g g ~
qq
o
~
0
gga~ggggg
0q.
~[
(.9
oo oo ooo oo oo ooo o~ o q q
'R.
80
110
140
]70
200
Temperature(C)
0 0 0 0
g g g g g g g ~ >
=o
e~
o
~gggggggg
II
ggggggg~gg
7
o
~ggg~ggggg
e'~
o
=
Q q o q q q o q
~ g g g g g g g g
"2.
gggggggggg
r.~
II
G)
o
"7
eq
105
488.9 C
437.5 C ~
210C
3.2. Characterization
BET nitrogen surface area of the catalyst sample
was about 180 m 2 g-t. Its nickel dispersion measured
by oxygen uptake at 25C using a pulse chromatographic technique was 0.30. These results show that
the amorphous NiB/SiO2 has larger surface area and
higher nickel dispersion.
Fig. 3 shows the XRD patterns of four NiB/SiO2
samples. The patterns of (b) and (c) were almost the
same. After subtracting the background spectrum of
SiO2, a broad peak at 20=45 was observed. This was
attributed to the NiB alloy in the amorphous state. The
pattern of (d) indicated that the amorphous state still
remained, but on the pattern of (e), the diffraction
peaks of some crystal, which was analyzed to be
nickel crystallite, had appeared. DSC spectra, as
_=
20
40
60
80
20()
Fig. 3. X-ray diffraction patterns of (a) SiO2, (b) original NiB/
SiO> (c) NiB/SiO2 after 500 h of hydrogenation at 120C, (d) NiB!
SiO2 treated in N2 for 2 h at 400C, and (e) NiB/SiO2 treated in N2
for 2 h at 450C.
100
200
300
400
500
600
Temperature(C)
Fig. 4. DSC spectra of NiB/SiO2.
106
Magnific~ion:100~.~
Magnii]cati~ln ~0 0 ( ~ [11)
$q~Or~m
Magnil]clllof~ IO00o O0
rD = F D X = kDPDPH2,
(3)
Ni2v3t2
107
Bls
852.0 eV
194.0 eV
Binding Energy(eV)
Fig. 6. XPS spectra of Nizp3/2 and BI~ in the NiB/SiO2 catalyst.
nitrogen flow-rate
simply by
PD oc VD :x FD,
(4)
rD = kDPn2 = k e x p ( - E / R T ) P H : ,
Plq2 :x v~q2,
(5)
1 ~m--I
n
= tc~r
D v.2.
(6)
(7)
(8)
(9)
rD = 2.6 10 -3 e x p ( - 8 3 5 / T ) P m
(10)
Table 2
Observed and calculated rates of reaction as a function of the
reaction temperature
T(C)
robs (10 6 m o l s - l )
real (10 6 m o l s 1)
80
100
3.03
3.78
3. l 8
3.61
120
4.17
4.05
140
160
4.38
4.78
4.48
4.92
108
1.0
0.8
0.6
0.4
0.2
1.1
1.2
1.3
1.4
1.5
1.6
Log Pm
Fig. 7. The logarithm of the CPD conversion vs. the logarithm of the CPD feed plots (conditions: PH2=0.2 atm, GHSV=24000 1).
0.8
0.6
X
o
0.4
0.2
140"C
o 160 C
NN~.%NN~eNN~Q
1.2
1.6
1.4
1.8
2.0
2.2
Log FCI,D
Fig. 8. The logarithm of the CPD conversion vs. the logarithm of the PH2 plots (conditions: P0=0.25 atm, GHSV=24000 i).
pentadiene pressure are 0.13 and 0.25 atm, respectively. Very good agreement was found between the
calculated and observed rates of reaction.
(11)
(12)
If ~D and KD are the surface coverage and adsorption coefficient of cyclopentadiene, respectively, and
the rate-determining step is Eq. (12), one may
write
(13)
~)D = K D P D / ( I + K D P D ) ,
rD = kD~DPH2 = kDKDPDPH2 / (1 + KDPD ).
is
strongly
(14)
4. Conclusions
It was shown that an amorphous nickel-boron alloy
supported on silica was very helpful for selective
hydrogenation of cyclopentadiene to cyclopentene
at low temperature in gas-solid phase. The catalyst
activity was very stable for a long time on stream. The
results in catalyst characterization showed that the
amorphous state was maintained over 80-120C. The
differential kinetic study revealed that the reaction
mechanism was of the Rideal-Eley type with cyclopentadiene strongly adsorbed on the catalyst. To our
109
Acknowledgements
This work was supported by the National Natural
Science Foundation of China and China Petrochemical Corporation.
References
[1] G. Natta, J. Polymer Sci. 51 (1961) 463.
[2] N. Calderon, R.L. Hinrichs, Chem. Tech. 4 (1974) 627.
[3] Goodyear Tire, Rubber, US Patent, 3751499 (1973),
3819734 (1974), 3915 891 (1975), 4 131 627 (1978); Gulf
Res. Dev., US Patent, 4062907 (1977); Kanegabuchi Chem.
Ind., Japan Kokai, 49-31642, 50-14657; Nissan Chem. Ind.,
Japan Kokai, 49-35358; Sakai Chem., Japan Kokai, 49125340; Shell. Inst. Res., Ger. Often., 2 127625 (1971).
[4] P. Kripylo, Chem. Tech. 28 (1976) 22.
[5] H. Sakamoto, K. Takasaki, Y. Harano, T. Imoto, J. Appl.
Chem. Biotechnol. 24 (1974) 759.
[6] H. Hiral, S. Komatsuzaki, N. Toshima, Bull. Chem. Soc. Jpn.
57 (1984) 488.
[7] V.M. Kothari, Ger. Often. 2315002 (1973); US Appl.,
250802 (1973).
[8] J.R. Bernerd, J. Chem. Phys. Chem. Biol. 74 (1977) 475.
[9l E.B. Fountain, Ger. Often. 2217625 (1970).
[10] G. Pajonk, Bull. Soc. Chem. Fr. (1975) 983.
[11] S. Yoshida, H. Yamashita, T. Funabiki, T. Yonezawa, J. Chem.
Soc., Faraday Trans. I. 80 (1984) 1435.
[12] A. Molnar, G.H. Smith, M. Bartok, Adv. Catal. 36 (1988)
329.
[13] J.F. Deng, X.P. Zhang, Appl. Catal. 37 (1988) 339.
[14] J.E Deng, X.P. Zhang, Solid State Ionics 32/33 (1989) 1006.
[15] D.K. lvana, Appl. Catal. 42 (1988) 121.
[16] J.E Deng, J. Yang, S.S. Sheng, H.R. Chen, G.X. Xing, J.
Catal. 150 (1994) 434.
[17] Y. Okamoto, Y. Nitta, T. Imanaka, S. Teranishi, J. Chem. Soc.,
Faraday Trans. 175 (1979) 2027.
[18] J.A. Schreifels, P.C. Maybury, W.E. Swartz, J. Catal. 65
(1980) 195.
[19] J. Tamaki, H. Takagaki, T. Imanaka, J. Catal. 108 (1987) 256.
[20] P. Kripylo, E Turek, Chem. Tech. 27 (1975) 605.
[21] J. Chaouki, C. Chavarie, Appl. Catal. 187 (1986) 199.
[22] E.K. Redeal, Concepts in Catalysis, Academic Press, London,
1980.