New synthesis routes for production of ε-caprolactam by ... - RWTH

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(IV) BP Chemical process 2. General Part Scheme-12: TechniChem Process. According to BP chemical process (Scheme-13), cyclohexanone is reacted with hydrogenperoxide (2:1 mixture) to form a 1,1-dihydroxydicyclohexylperoxide in the presence of an organic solvent and stabilizer. In a second step, the 1,1- dihydroxydicyclohexylperoxide reacts with ammonia to 1,1-peroxydicyclohexylamine, which is transformed to caprolactam and cyclohexanone with the help of lithium halogenides [23-25]. The great advantage of this process is that no by-products are formed. However, this process was not commercialized until now. Scheme-13: BP 1,1-dihydroxydicyclohexylperoxide process. 18
2.3. New synthesis methods 2. General Part As caprolactam is an intermediate product with growing demand, there is an extensive research ongoing for new synthesis processes, which are economically favorable and environmentally friendly. The main aim of the research in the new synthesis methods is avoidance of the production of large amount of ammonim sulfate, which can be achieved by prevention of the formation of any salt or by the replacement of ammonium sulfate by a more valuable ammonium salt. 2.3.1. The catalytic gas phase Beckmann rearrangement reaction To overcome by-product formation and reactor corrosion problems, more economic and environmentally friendly process technology has been developed. In 1938, DuPont proposed a process in which cyclohexanone oxime vapor was passed over catalysts such as silica, alumina titania or magnesia, preferably in the presence of ammonia, at a temperature of 250-350 °C [26]. In the early 1950’s, Dawydoff (Leuna- Werke) showed that boron oxide catalysts gave high yields in the vapor-phase Beckmann rearrangement [27]. The gas phase Beckmann rearrangement reaction was also carried out over different solid acid catalysts [28-29]. Previous studies showed that solid acids such as tungsten oxide [30], silica-tantalum oxide [31], titanium oxide [32], and boron- silica [33] are active catalysts. However, the application of all these catalysts results in low selective for CL and exhibited fast deactivation for the reaction. Recently, zeolites have been used as solid acid catalysts for Beckmann rearrangement reaction have been used [11, 22, 34-40]. Several potential materials along with all these materials such as TS-1 [41], SAPO 11,[42], Beta, Y [43-44] ZSM-5, and monolithic silicalite [22, 35-36, 40, 45-47] catalysts were applied for this reaction under gas phase as well as in liquid 19
Page 1 and 2: New synthesis routes for production
Page 3 and 4: This work reported here has been ca
Page 5 and 6: Contents 1. Introduction and Object
Page 7 and 8: Contents 5.2.6 Effect of H2O2/cyclo
Page 9 and 10: Abbreviations Part from chemical sy
Page 11 and 12: 1. Introduction and Objectives 1. I
Page 13 and 14: 1. Introduction and Objectives econ
Page 15 and 16: 2. General Part 2. General Part 2.1
Page 17 and 18: 2. General Part Scheme 1: Current c
Page 19 and 20: Step 1: Step 2: Cyclohexanone 2 NO
Page 21 and 22: 2. General Part alumina carrier. Th
Page 23 and 24: +HNO3 -H 2O 2. General Part 13 NO 2
Page 25 and 26: 2. General Part (NH4)2SO4 could be
Page 27: (II) UCC Process 2. General Part Sc
Page 31 and 32: 2. General Part selectivity for cap
Page 33 and 34: 2. General Part polymeric species a
Page 35 and 36: 2. General Part by oxidation with e
Page 37 and 38: 2. General Part different research
Page 39 and 40: 2. General Part The first step in t
Page 41 and 42: 2. General Part cyclohexanone oxime
Page 43 and 44: 2. General Part alkylbenzenes, prod
Page 45 and 46: 2. General Part Figure -2: Possible
Page 47 and 48: 2. General Part Figure-3: Possible
Page 49 and 50: 3. Gas phase Beckmann rearrangement
Page 51 and 52: 3.1. Catalysts characterization res
Page 55 and 56: 3.1.2 N2 Physisorption 3.1. Catalys
Page 77 and 78: 3.1.9. Pyridine FT-IR 3.1. Catalyst
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3.1. Catalysts characterization res
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3.2. Catalytic results and discussi
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C.hexanone oxime conversion % 100 9
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Cyclohexanone oxime conversion % Cy
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Cyclohexanone oxime conversion % 10
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Conversion/ selectivity% 100 95 90
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Conversion/selectivity% 100 90 80 7
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Conversion/ selectivity (%) 100 80
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Uv/mg Weight loss % 0.2 0.1 0.0 -0.
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DESIGN-EXPERT Plot Actual Factors:
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DESIGN-EXPERT Plot Actual Factors:
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4. Summary and Outlook 4. Summary a
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4. Summary and Outlook indicated th
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4. Summary and Outlook loss of the
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5. Liquid phase ammoximation reacti
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% 5. Liquid phase ammoximation reac
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6. Summary and Outlook 6. Summary a
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6. Summary and Outlook. oligomers a
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6. Summary and Outlook. Ammonia TPD
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6. Summary and Outlook. Reaction re
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7. Materials and Methods 7. Materia
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7. Materials and Methods 7.1.1 Hydr
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7. Materials and Methods 7.1.4 Hydr
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7. Materials and Methods mixed and
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7. Materials and Methods for the mo
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7. Materials and Methods equilibrat
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7. Materials and Methods NH3-TPD of
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7. Materials and Methods Carrier ga
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7. Materials and Methods 7.3.2 Ammo
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7. Materials and Methods Figure: 2-
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8. References 8. References [1] P.
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8. References [33] S. Sato, K. Urab
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8. References [66] S. Van Donk, A.
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8. References [98] C. Yan, J. Fraga
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8. References [134] J. M. R. Gallo,
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8. References [168] G. P. Heitmann,
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8. References [195] Beck, J.S., Var
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New synthesis routes for production of ε-caprolactam by ... - RWTH

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