DOI: 10.1039/C3CY00568B
Catalysis Science & Technology
were added into the reactor, the mixture of 40 ml H O, 112.8
Testing Center of Sichuan University are cordially
acknowledged. The suggestions by the reviewers were highly
appricated.
2
mmol NH •H O and 19.8 mmol H O was fed to the reaction
3
2
2
2
-
1
system with 0.1 ml·min by peristaltic pump after the reactor was
heated to 60°C. Then, the reaction mixture was cooled and
5
0
5
0
5
0
5
0
centrifuged to separate Cu/h-TS-1 catalyst. Based on optimized 60 Notes and references
3
conditions in our pervious work , 0.05 g NaVO , 25 ml
3
a
Key Laboratory of Green Chemistry and Technology, Ministry of
CH COOH and 2.82 mmol benzene were successively added to
the reactor, the amination of benzene was carried out in 1.5 h at
3
Education, College of Chemistry, Sichuan University, 29 Wangjiang Road,
School of life sciences ,Guizhou Normal University, 116 Baoshan North
Road, Guiyang 550001, China
6
0°C. An aniline yield of about 1.2%, with a selectively of 91.6%
b
65
1
1
2
2
3
3
4
to aniline, was obtained. Meanwhile the gaseous products were
monitored using an on-line gas mass spectrometers analysis
†
Electronic Supplementary Information (ESI) available: activity data.
See DOI:10.1039/b000000x/
system (HPR-20QIC). N , N O and O were detected in the
2
2
2
whole reaction period. V. Cortés Corberán et al had evidenced
1 S. A. Axon, WO Pat., 99/10 311, 1999.
that the hydroxylamine produced could further react with 70 2 H. Yuzuwa and H. Yoshida,Chem. Commun., 2010, 46, 8854.
3
L. F. Zhu, B. Guo, D. Y. Tang, X. K. Hu, G. Y. Li and C. W. Hu, J.
Catal., 2007, 245, 446.
A.Hagemeyer, R. Borade, P. Desrosiers, S. Guana, D. M. Lowea, D. M.
Poojary, H. Turner, H. Weinberg, X. P. Zhou, R. Armbrust , G. Fengler
and U. Notheis, Appl. Catal., A, 2002, 227, 43.
hydrogen peroxide to give N and N O in the presence or absence
2
2
3
8
of TS. N O was also detected in the catalytic amination using
2
4
HAc-H O as medium and hydroxylamine as aminating agent in
2
3
our previous work. The result showed that aniline was produced
75
without Cu/h-TS-1 and the gaseous products agreed with the
5
[a] S.Singha and K. M. Parida, Catal. Sci. Technol., 2011, 1, 1496; [b]
K. M. Parida, D. Rath and S. S. Dash, J. Mol. Catal. A: Chem., 2010,
3
,41
above literature report
, suggesting hydroxylamine had
3
2
18, 85; [c] K. M. Parida , S. S. Dash and S. Singha, Appl. Catal., A,
008, 351, 59.
produced in the reaction system.
To clearly determine whether the aniline was generated from
8
8
9
9
0
5
0
5
6
7
8
J. P. Wibaut, Berichte, 1917, 50, 541.
J. T. Anders, US Pat., 2009/0292144, 2009.
[a] L. Schmerling, US Pat., 2 948 755, 1960; [b] E. N. Squire, US Pat.,
direct amination of benzene over NaVO . The reaction was
3
carried out using 0.05 g NaVO instead of 2.5 wt % Cu/h-TS-1
3
3
929 899, 1975; [c] E. N. Squire, US Pat., 3 919 155, 1975; [d] T. W.
under the aforementioned optimized conditions, while no aniline
was obtained.
DelPesco, US Pat., 4 001 260, 1977; [e] T. W. DelPesco, US Pat., 4
031 106, 1977; [f] Desrosiers, P. Guana, S. Hagemeyer, Lowea, A. D.
Lugmair, M. C. Poojary, D. M. Turner, H. Weinberg, H. Zhou, X. P.
Armbrust, R. Fengler, G. Notheis and U. Notheis, Catal. Today.,
To investigate whether the aniline was obtained from one-step
amination of benzene with hydroxylamine over Cu/h-TS-1. The
2
003, 81, 319.
2
9
F. V. Laar, US Pat., 2009/0203941, 2009.
2
2
10 [a] N. Hoffmann and M. Muhler, Catal. Lett., 2005, 103, 155; [b] N.
Hoffmann, E. L, Niklas A. Breuer and M. Muhler, ChemSusChem,
2008, 1, 393.
-
1
solution (0.29 mmol·ml ) under the aforementioned optimized
conditions. No aniline was detected in the reaction. When 4.0
mmol H O was continuously added into the above reaction
11 [a] H. E. Stitt, WO Pat., 00/09 473, 2000; [b] H. E. Stitt, WO Pat.,
2
2
0
0/69 804, 2000; [c] V. A. Durante, US Pat., 5 861 536, 1999.
mixture, an aniline yield of about 29.8% with phenol (13.2%),
DHB (4.3%) and trace amount of nitrobenzene, with a selectively
of 63.0% to aniline, was obtained.
12 F. V. Laar , US Pat., 7 741 522, 2010.
1
3 [a] J. Becker and W. F. Hölderich, Catal. Lett., 1998, 54, 125; [b] F.
Hölderich, DE Pat., DE 19634 110, 1998.
In addition, owing to the production of phenol in the reaction
system, the reaction was carried out using phenol as the original
material in order to confirm whether phenol was the intermediate
in the reaction. The result showed that no aniline or hydroxy-
substitued anilines were detected, which agreed well with the
14 [a] Y.S. Xia, L.F. Zhu, G.Y. Li and C.W. Hu, Acta Phys.-Chim. Sin.,
2005, 21, 1337; [b] C. W. Hu, L. F. Zhu and Y. S. Xia, Ind. Eng.
Chem. Res., 2007, 46, 3443.
1
1
00
05
1
5 T. Chen, Z. J. Fu, L. F. Zhu, C. W. Hu and A. M. Tian, Acta Chim.
Sin., 2003, 61, 1701.
1
6 C.W. Hu, L.F. Zhu and Y.S. Xia, CN Pat., 155555921, 2004.
3
,17
previous work.
This confirmed that the possible intermediate
17 B. Guo, Q. Zhang, G. Y. Li, J. Y. Yao and C. W. Hu, Green Chem.,
2012, 14, 1880.
for aniline formation was hydroxylamine instead of phenol.
1
8 C. Buchaly, P. Kreis and A. Górak, Ind. Eng. Chem. Res., 2012, 51,
4
. Conclusions
891.
1
9 J. Castor González and J. R. Fair, Ind. Eng. Chem. Res., 1997, 36,
4
5
In summary, the RD was successfully applied to shift the reaction
3833.
equilibrium towards aniline in the direct amination of benzene to 110 20 Gildert, US Pat., 5 773 670, 1998.
2
1 W. B. Fan, R. G. Duan, T. Yokoi, P. Wu, Y. Kubota and T. Tatsumi, J.
aniline. Under optimized conditions, desired aniline yield (12.4%)
with excellent selectivity (84.7%) was obtained. The entire
process was simple, since the operation was performed under
approximately atmospheric pressure at low temperature. Based on 115
the experimental results, a probable catalytic pathway of benzene
ammoxidation to aniline via hydroxylamine over h-TS-1 or metal
doped h-TS-1 was proposed.
Am. Chem. Soc., 2008, 130, 10150.
2
2 H. C. Xin, J. Zhao, S. T. Xu, J. P. Li, W. P. Zhang, X. W. Guo, E. J.
M. Hensen, Q. H. Yang and C. Li, J. Phys. Chem. C, 2010, 114,
6553.
5
0
23 Y. Cheneviere, F. Chieux, V. Caps, and A. Tuel, J. Catal., 2010, 269,
61.
4 S. S. Li, A. F. Zhang, M. Liu and X. W. Guo, Chin. Chem. Lett., 2011,
2, 303.
1
2
2
1
20 25 [a] Taramasso et al, US Pat., 4 410 501, 1983; [b] S. K. Fan, J. J. Xue,
Acknowledgements
T. Yu, D. Q. Fan, T. Hao, M. Q. Shen and W. Li, Catal. Sci. Technol.,
2
013, DOI: 10.1039/c3cy00339f; [c] Y. Wang, Y. M. Liu, X. H. Li, H.
5
5
Financial support from the NSFC (No. 21172157 and
H. Wu, M. Y. He and Peng Wu, J. Catal., 2009, 266, 258.
2
1021001) of China, and technical support by Analytic and
8
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