RESEARCH ARTICLE

One-step synthesis of ϵ-caprolactam via the liquid phase catalytic nitrosation of cyclohexane in the presence of concentrated sulfuric acid

  • Kuiyi YOU ,
  • Fangfang ZHAO ,
  • Xueyan LONG ,
  • Pingle LIU ,
  • Qiuhong AI ,
  • Hean LUO
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  • School of Chemical Engineering, Xiangtan University, Xiangtan 411105, China

Received date: 24 Jul 2012

Accepted date: 18 Sep 2012

Published date: 05 Dec 2012

Copyright

2014 Higher Education Press and Springer-Verlag Berlin Heidelberg

Abstract

A simple and efficient approach for the synthesis of ϵ-caprolactam via the liquid phase nitrosation of cyclohexane and nitrosyl sulfuric acid in the presence of concentrated sulfuric acid has been developed. A series of novel AlVPO composites were prepared by an impregnation method and the composites were then employed to catalyze the nitrosation reaction of cyclohexane and nitrosyl sulfuric acid. Compared to the reaction using fuming sulfuric acid, the selectivity for the desired product was significantly improved using this one-step catalytic process. This method affords a shortcut to prepare ϵ-caprolactam and its analogs from cyclohexane.

Cite this article

Kuiyi YOU , Fangfang ZHAO , Xueyan LONG , Pingle LIU , Qiuhong AI , Hean LUO . One-step synthesis of ϵ-caprolactam via the liquid phase catalytic nitrosation of cyclohexane in the presence of concentrated sulfuric acid[J]. Frontiers of Chemical Science and Engineering, 2012 , 6(4) : 389 -394 . DOI: 10.1007/s11705-012-1218-0

Acknowledgments

The authors are grateful for the financial support for this work by the National Natural Science Foundation of China (Grant Nos. 21006081 and 21276216), the Scientific Research Fund of Hunan Provincial Education Department (Nos. 11B122, 09K035 and 08B087), and the Natural Science Foundation of Hunan Province (No. 11JJ3024).
1
Ichihashi H, Sato H. The development of new heterogeneous catalytic processes for the production of ϵ-caprolactam. Applied Catalysis A, General, 2001, 221(1–2): 359–366

DOI

2
Chaudhari K, Bal R, Chandwadkar A J, Sivasanker S. Beckmann rearrangement of cyclohexanone oxime over mesoporous Si-MCM-41 and Al-MCM-41 molecular sieves. Journal of Molecular Catalysis A, Chemical, 2002, 177(2): 247–253

DOI

3
Ishida M, Suzuki T, Ichihashi H, Shiga A. Theoretical study on vapour phase Beckmann rearrangement of cyclohexanone oxime over a high silica MFI zeolite. Catalysis Today, 2003, 87(1–4): 187–194

DOI

4
Zhang Y J, Wang Y Q, Bu Y F, Mi Z T, Wu W, Min E Z, Han S, Fu S B. Beckmann rearrangement of cyclohexanone oxime over Hβ zeolite and Hβ zeolite-supported boride. Catalysis Communications, 2005, 6(1): 53–56

DOI

5
Heitmann G P, Dahlhoff G, Niederer J P, Hoelderich W F. Active sites of a [B]-ZSM-5 zeolite catalyst for the beckmann rearrangement of cyclohexanone oxime to caprolactam. Journal of Catalysis, 2000, 194(1): 122–129

DOI

6
Heitmann G P, Dahlhoff G, Hoelderich W F. Catalytically active sites for the beckmann rearrangement of cyclohexanone oxime to ϵ-caprolactam. Journal of Catalysis, 1999, 186(1): 12–19

DOI

7
Singh P S, Bandyopadhyay R, Hegde S G, Rao B S. Vapour phase beckmann rearrangement of cyclohexanone oxime over SAPO-11 molecular sieve. Applied Catalysis A, General, 1996, 136(2): 249–263

DOI

8
Meng F, Wang Y, Wang L, Yang R, Zhang T. Influence of Br and Na+ in synthesis of Silicalite-1 on catalytic performance in vapor phase Beckmann rearrangement of cyclohexanone oxime. Journal of Molecular Catalysis A, Chemical, 2011, 335(1–2): 105–111

DOI

9
Bordoloi A, Halligudi S B. Catalytic properties of WOx/SBA-15 for vapor-phase Beckmann rearrangement of cyclohexanone oxime. Applied Catalysis A, General, 2010, 379(1–2): 141–147

DOI

10
Pillai S K, Gheevarghese O, Sugunan S. Catalytic properties of V2O5/SnO2 towards vapour-phase Beckmann rearrangement of cyclohexanone oxime. Applied Catalysis A, General, 2009, 353(1): 130–136

DOI

11
Zhang D, Wang R, Yang X. Beckmann rearrangement of cyclohexanone oxime over Al-MCM-41 and P modified Al-MCM-41 molecular sieves. Catalysis Communications, 2011, 12(6): 399–402

DOI

12
Tatsumi T, Jappar N. Ammoximation of cyclic ketones on TS-1 and amorphous SiO2-TiO2. Journal of Catalysis, 1996, 161(2): 570–576

DOI

13
Bars J L, Dakka J, Sheldon R A. Ammoximation of cyclohexanone and hydroxyaromatic ketones over titanium molecular sieves. Applied Catalysis A, General, 1996, 136(1): 69–80

DOI

14
Liu T F, Meng X K, Wang Y Q, Liang X H, Mi Z T, Qi X J, Li S Y, Wu W, Min E Z, Fu S B. Integrated process of H2O2 generation through anthraquinone hydrogenation-oxidation cycles and the ammoximation of cyclohexanone. Industrial & Engineering Chemistry Research, 2004, 43(1): 166–172

DOI

15
Thomas J M, Raja R. Catalytically active centres in porous oxides: designand performance of highly selective new catalysts. Chemical Communications, 2001, 36(8): 675–687

DOI

16
Ritz J, Fuchs H, Kieczka H, Moran W C. Ullman’s Encyclopedia of Industrial Chemistry. New York: VCH, Weinhein. 1986, A5: 31

17
You K Y, Wu B H, Mao L Q, Yin D L, Liu P L, Luo H A. A novel route to one-step formation of ϵ-caprolactam from cyclohexane and nitrosyl sulfuric acid catalyzed by VPO composites. Catalysis Letters, 2007, 118(1–2): 129–133

DOI

18
You K Y, Mao L Q, Chen L, Yin D L, Liu P L, Luo H A. One-step synthesis of ϵ-caprolactam from cyclohexane and nitrosyl sulfuric acid catalyzed by VPO supported transition metal composites. Catalysis Communications, 2008, 9(11–12): 2136–2139

DOI

19
Mao L Q, Chen L, Wu B H, Yin D L, You K Y, Liu P L, Luo H A. One-step synthesis of ϵ-caprolactam by the liquid phase nitrosation of cyclohexane over the catalysts containing CH3COO- or —COOH. Chemical Research in Chinese Universities, 2008, 24(2): 246–248

DOI

20
Mao L Q, Wu B H, Yin D L, You K Y, Liu P L, Luo H A. A novel approach for one-step forming ϵ-caprolactam from cyclohexane nitrozation catalyzed by transition metal salt. Chinese Chemical Letters, 2007, 18(3): 269–271

DOI

21
Liu P L, Xie H, You K Y, Hao F, Li X F, Luo H A. Preparation of SiO2-Al2O3 and its supported Co3O4 catalysts for nitrosation of cyclohexane. Catalysis Letters, 2010, 136(1–2): 150–154

DOI

22
Hao F, Zhong J, Liu P L, You K Y, Wei C, Liu H J, Luo H A. Preparation of mesoporous SiO2-Al2O3 supported Co or Mn catalysts and their catalytic properties in cyclohexane nitrosation to caprolactam. Journal of Molecular Catalysis A, Chemical, 2011, 351: 210–216

DOI

23
Hutchings G J, Higgins R. Effect of promoters on the selective oxidation of n-butane with vanadium-phosphorus oxide catalysts. Journal of Catalysis, 1996, 162(2): 153–168

DOI

24
McCormick R L, Alptekin G O, Herring A M, Ohno T R, Dec S F. Methane partial oxidation over vanadyl pyrophosphate and the effect of Fe and Cr promoters on selectivity. Journal of Catalysis, 1997, 172(1): 160–169

DOI

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