Paper
RSC Advances
a
Table 5 The recycle of K–La–Ni/SEP in ADN hydrogenation
3 P. Bassler, H. Luyken, G. Achhammer, T. Witzel, E. Fuchs,
R. Fischer and W. Schnurr, US Pat., 5717090A, 1998.
R. Sheldon, Green Chem., 2000, 2, G1–G4.
Selectivity (%)
4
Run
number
ADN conversion
(%)
ACN and
HMDA
5 M. Serra, P. Salagre, Y. Cesteros, F. Medina and J. E. Sueiras,
Solid State Ionics, 2000, 134, 229–239.
ACN
HMDA
ACH
6
7
M. Serra, J. Catal., 2002, 209, 202–209.
M. Serra, P. Salagre, Y. Cesteros, F. Medina and J. E. Sueiras,
Appl. Catal., A, 2004, 272, 353–362.
1
2
3
4
92.36
86.35
84.26
76.32
66.50
62.14
60.36
54.67
24.85
27.60
25.74
22.69
8.65
10.26
18.90
22.64
91.35
89.74
81.10
77.36
8 L. Zhao, C. Y. Wang, J. X. Chen and J. Y. Zhang, Chin. J. Chem.
Eng., 2007, 18, 685–688.
9
a
Reaction conditions: stirring rate, 1000 rpm; PH2, 2.0 MPa; reaction
time, 360 min; reaction temperature, 393 K; ethanol, 50 mL; and, 5 g;
catalyst, 1 g.
S. Alini, A. Bottino, G. Capannelli, A. Comite and S. Paganelli,
Appl. Catal., A, 2005, 292, 105–112.
1
1
1
1
0 D. Tichit, R. Durand, A. Rolland, B. Coq, J. Lopez and
P. Marion, J. Catal., 2002, 211, 511–520.
1 X. B. Yu, H. X. Li and J. F. Deng, Appl. Catal., A, 2000, 199,
HMDA reaches to 91.32% under mild reaction conditions of 393
1
91–198.
2 H. X. Li, Y. P. Xu, H. Li and J. F. Deng, Appl. Catal., A, 2001,
16, 51–58.
3 F. Medina, P. Salagre, J. Sueiras and J. Fierro, J. Mol. Catal.,
991, 68, L17–L20.
The recycle of K–La–Ni/SEP has been investigated and the 14 F. Medina, P. Salagre, J. E. Sueiras and J. L. G. Fierro, J. Mol.
results are listed in Table 5. Aer each reaction, K–La–Ni/SEP
Catal., 1993, 81, 387–395.
was separated by ltration, dried at room temperature and 15 F. Medina, P. Salagre, J. E. Sueiras and J. L. G. Fierro, Solid
reduced at 673 K for 4 h. It can be seen from Table 5 that the
State Ionics, 1993, 59, 205–210.
catalytic activity decreases slightly in the second and third runs. 16 F. Medina, P. Salagre, J. E. Sueiras and J. L. G. Fierro, J. Chem.
The selectivity to ACN is above around 60%, and the total
Soc., Faraday Trans., 1993, 89, 3507–3512.
selectivity to ACN and HMDA is greater than 80%. However, the 17 F. Medina, P. Salagre, J. E. Sueiras and J. L. G. Fierro, Appl.
2 3
K and 2.0 MPa. Compared with K–Ni/a-Al O , the reaction
temperature over K–La–Ni/SEP is reduced by 30 K.
2
3.3 The recycle of the catalysts
1
activity and the selectivity to ACN decrease obviously when the
catalyst was used for the fourth times.
Catal., A, 1993, 99, 115–129.
18 F. Medina, P. Salagre, J. E. Sueiras and J. L. G. Fierro, J. Chem.
Soc., Faraday Trans., 1993, 89, 3981–3986.
1
9 F. Medina, P. Salagre, J. E. Sueiras and J. L. G. Fierro, J. Chem.
Soc., Faraday Trans., 1994, 90, 1455–1459.
4
Conclusions
Potassium and lanthanum promoted nickel based sepiolite 20 M. C. Cotting, L. Gilbert and P. Leconte, US Pat., 5981790,
catalysts were prepared and used in the ADN hydrogenation.
1999.
The potassium could neutralize some acid sites on the catalyst 21 S. B. Ziemecki, US Pat., 5151543, 1992.
and inhibit the formation of the ACH by-product. The 22 M. Harper, WO Pat., 0027526A1, 2000.
lanthanum could efficiently reduce the diameter and improve 23 R. P. Beatty and R. A. Paciello, US Pat., 5554778, 1996.
the dispersion of the active nickel particles. Among these 24 R. P. Beatty and R. A. Paciello, US Pat., 5559262, 1996.
catalysts, K–La–Ni/SEP exhibits the best selectivity to ACN and 25 R. P. Beatty and R. A. Paciello, US Pat., 5599962, 1997.
HMDA at a higher ADN conversion. The selectivity to ACN and 26 H. G. Liao, S. H. Liu, F. Hao, P. L. Liu, K. Y. You, D. D. Liu and
HMDA could reach to 91.32% at 92.56% conversion of ADN
under mild conditions of 393 K and 2.0 MPa.
H. a. Luo, React. Kinet., Mech. Catal., 2013, 109, 475–488.
27 J. A. Anderson, S. E. Falconer and M. Gal ´a n-Fereres,
Spectrochim. Acta, Part A, 1997, 53, 2627–2639.
2
8 F. M. Bautista, J. M. Campelo, A. Garcia, R. Guarde n˜ o,
D. Luna and J. M. Marinas, J. Mol. Catal. A: Chem., 1996,
104, 229–235.
Acknowledgements
This work was supported by NSFC (21276218, 21306160),
Project of Hunan Provincial Education Department (14C1093, 29 S. Damyanova, L. Daza and J. L. G. Fierro, J. Catal., 1996, 159,
14C1097) and Project of Hunan Provincial Science and Tech-
150–161.
nology Department (2015GK1060).
30 S. Liu, M. Chen, L. Chu, Z. Yang, C. Zhu, J. Wang and
M. Chen, Int. J. Hydrogen Energy, 2013, 38, 3948–3955.
3
3
1 Y. Ma and G. Zhang, Chem. Eng. J., 2016, 288, 70–78.
2 K. N u´ n˜ ez, R. Gallego, J. M. Pastor and J. C. Merino, Appl. Clay
Sci., 2014, 101, 73–81.
References
1
H. Kajikuri, M. Kitamura and Y. Higashio, US Pat., 5304643,
992.
1
3
3 F. Mares, J. E. Galle, S. E. Diamond and F. J. Regina, J. Catal.,
2
R. Fischer, P. Bassler, H. Luyken, F. Ohlbach, J. P. Merger,
1988, 112, 145–156.
A. Ansmann, A. Rehnger and G. Voit, US Pat., 6359178B1,
2002.
This journal is © The Royal Society of Chemistry 2016
RSC Adv., 2016, 6, 60933–60939 | 60939