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Development of a Process for the Preparation of Linalool from Cis -2-Pinanol

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Development of a Process for the Preparation of Linalool from Cis -2-Pinanol 1 DEVELOPMENT OF A PROCESS FOR THE PREPARATION OF LINALOOL FROM CIS -2-PINANOL Subash Ramnarain Buddoo Thesis submitted in fulfilment of the requirements for the degree DOCTOR TECHNOLOGIAE In the faculty of Applied Science at the NELSON MANDELA METROPOLITAN UNIVERSITY June 2008 Promoter : Prof. B. Zeelie Co-promoter : Dr. J. Dudas 2 ACKNOWLEDGEMENTS The author wishes to express his sincere appreciation to: • My promoters, Prof. B. Zeelie and Dr. J. Dudas for their assistance, guidance and encouragement to conclude this project; • The Department of Science and Technology for funding the project under the Support Programme for Industrial Innovation (SPII); • The THRIP fund for providing funds for the purchase of equipment required for the laboratory experimental investigations; • Teubes Pty. Ltd. for financial support, provision of starting material (CST and α-pinene) and for permission to use this material for a thesis; • S. Farnworth for the management of the CST project; • N. Siyakatshana for his assistance with the reaction kinetics and computer modelling of the process; • B. Cowan for assistance with the GC-MS analysis; and • My wife (Shelina), son (Kavish) and daughter (Sarisha) for their encouragement, patience and tolerance. 3 SUMMARY Linalool is a key intermediate for the production of important fragrance chemicals such as geraniol, nerol, geranial, and neral. Linalool can be produced via a two-step process from α-pinene which is a major component of crude sulphated turpentine (CST) a foul-smelling, volatile waste product of the pulp and paper industry. The key step in this process is the pyrolysis step which involves the isomerisation of cis -2- pinanol to linalool and requires high temperatures (600-650°C) and is not very selective due to the decomposition of the product itself under these conditions. A client of the CSIR, Teubes Pty. Ltd., is a manufacturer of flavour and fragrance compounds for the local and international fragrance market and expressed an interest in producing linalool since the company would then gain access to other valuable fragrance chemicals via relatively simple processes. Earlier work conducted by AECI, R & D did not meet with much success since the selectivity to linalool was very poor and the process could hardly be deemed as scalable. The main objective of this project was therefore to develop a process for the selective isomerisation of cis -2-pinanol to linalool with minimum by-product formation and using process equipment that could be scaled to full-scale production. Since cis -2- pinanol could not be purchased in sufficient quantities for process development, a process had to be developed for the bench-scale preparation of kilogram quantities of cis -2-pinanol from α-pinene obtained from the client. Although this synthesis formed a minor part of this investigation, several process improvements and innovations were introduced to produce high quality cis -2-pinanol, in very good yields at kilogram scale. A major part of this investigation was the design and set up of a pyrolyis rig capable of operating at elevated temperatures (400 - 750°C) for the evaluation of various process parameters. Various vaporizer, reactor, and condensation systems were evaluated for their ability to cope with the demanding conditions on a consistent basis. The initial part of the investigation was a screening exercise to evaluate various process parameters as well as solvents, materials of construction, catalysts, etc. A comprehensive statistical design was also conducted to determine the critical process parameters and the model obtained was used to predict the optimum conditions 4 required for the preparation of in-specification product on a consistent basis. These conditions were used in the preparation of a 1kg sample which was required by the client for market evaluation purposes. The use of a novel microreactor system was also evaluated for the pinanol pyrolysis reaction. To our knowledge, this is the first time that a microreactor has been successfully used for this type of reaction in the Fragrance industry and a patent application is being filed by the CSIR. The kinetics of the reaction in both the tubular reactor system and the microreactor system was investigated. Computer modelling studies on both the systems were also conducted. The raw material cost to produce a kilogram of linalool is $1.40. There is a significant margin of 60.8% between the raw material cost of linalool and the current selling price ($3.57/kg). This clearly indicates that the project is potentially feasible from an economic point of view and we can now proceed with confidence to the next stage which is the engineering design, building and commissioning of the large scale pyrolysis rig. The rest of the process steps will be conducted on existing equipment currently present at the CSIR’s large scale facility (Imbiza in Isando, Gauteng). KEYWORDS Linalool, crude sulphated turpentine (CST), Paper and pulp industry, α-pinene, cis - pinane, pinane-2-hydroperoxide, cis -2-pinanol, tubular reactor, pyrolysis, isomerisation, vaporizer, condensation system, microreactor, computer modelling 5 CONTENTS 1 Introduction............................................................................................................8 1.1 Historical Background ...................................................................................8 1.2 History of Linalool.......................................................................................10 1.3 Problem statement........................................................................................11 1.4 The Global Fragrance Industry....................................................................11 1.5 The Fragrance Industry in South Africa ......................................................16 1.6 Aroma Chemicals from Turpentine .............................................................18 1.6.1 Turpentine............................................................................................18 1.6.2 Aroma Chemicals.................................................................................20 1.6.3 Feedstock Analysis ..............................................................................21 1.7 Commercial Production of Terpenoids – General Considerations ..............24 1.7.1 Safety ...................................................................................................25 1.7.2 Environment.........................................................................................26 1.7.3 Purity....................................................................................................29 1.7.4 Reproducibility ....................................................................................31 1.7.5 Capacity ...............................................................................................31 1.7.6 Cost......................................................................................................32 1.7.7 Sustainability........................................................................................34 1.8 Chemistry.....................................................................................................35 1.8.1 Definitions and Classification..............................................................35 1.8.2 The Isoprene Rule................................................................................37 1.8.3 Nomenclature.......................................................................................39 1.8.4 Acyclic Monoterpenoids......................................................................42 1.8.5 Bicyclic Monoterpenoids.....................................................................58 1.9 Commercial Production of Terpenoids including Linalool .........................77 1.9.1 Fragrance Ingredients derived from Terpenoids..................................77 1.9.2 Interconversion of the Five Key Terpenoids .......................................79 1.9.3 Commercial Aspects............................................................................81 1.9.4 Linalool Production/Synthesis.............................................................82 1.10 Zeolites as Catalysts.....................................................................................97 1.11 Microreactors...............................................................................................98 1.12 Equipment Considerations.........................................................................100 1.12.1 Introduction........................................................................................100 1.12.2 Overall Equipment.............................................................................101 1.12.3 Generation of Feed Streams...............................................................102 1.12.4 Product Condensation and Sampling.................................................106 1.13 Technology: Production of Terpene aroma chemicals ..............................107 1.13.1 South African Market Analysis .........................................................107 1.13.2 Conclusion .........................................................................................111 1.14 Feasibility of the Production of Terpene Aroma Chemicals .....................111 1.14.1 Affordable Capital .............................................................................111 1.14.2 Single Year Costing Model................................................................113 1.14.3 Capital Cost........................................................................................114
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