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The Reductive Amination of Ethanol Using Supported Metal Catalysts

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The Reductive Amination of Ethanol Using Supported Metal Catalysts The Reductive Amination of Ethanol using Supported Metal Catalysts By Gary Stanton Sewell- BSc (Chern. Eng.) Submitted to the University of Cape Town in fulfilment of the requirements for the degree of '• DOCTOR OF PHILOSOPHY University of Cape Town Department of Chemi~al Engineering 14 August 1996 University of Cape Town Rondebosch Cape Town South Africa ---"----""_______ " __ The copyright of this thesis vests in the author. No quotation from it or information derived from it is to be published without full acknowledgement of the source. The thesis is to be used for private study or non- commercial research purposes only. Published by the University of Cape Town (UCT) in terms of the non-exclusive license granted to UCT by the author. University of Cape Town Acknowledgements Acknowledgements I would like to thank my supervisors Dr Eric van Steen and Professor Cyril O'Connor for their guidance and encouragement without which this thesis would not have been possible. My thanks also go to Dr Klaus Moller for the fruitful discussions and to Professor Mark Dry for his help with aspects of metal catalysis. I would like to thank Rob for the great times, Tony for his friendship, Jannie for his cool hairstyle and Rein for having a comfortable couch. Thanks to Dave for introducing me to the finer intricacies of toolboxes, to Ashley for his unending optimism and to Peter for always losing at pool. To the II Young Ones II, Chappie, St. John, Frank, Andrew, Mary and Frans, thanks for the great parties and may the department survive you. To the catalysis ladies Pam and Leslie, thank you for all of your help with ordering and with the literature. Also to the electrical and mechanical workshops for their help in constructing my rig and to the cleaner staff for preventing my lab from becoming a Class 3 hazard. Special thanks also to Katarina for all the chemisorption work. I would like to thank the FRD and the Catalysis Research Unit for postgraduate funding and AECI, especially Norbert Behrens, for allowing me the time to complete my postgraduate studies. Lastly, I wish to thank my parents Keith and Maureen who have supported me throughout and Debbie for being such a great sister. Synopsis 11 Synopsis Silica supported cobalt, nickel and copper are efficient catalysts for the reductive amination of ethanol using anunonia. High selectivity to ethylamine product was obtained between reaction temperatures of 140 and 200'C, between anunonia to ethanol molar ratios ranging from 1 to 4 and between hydrogen to ethanol molar ratios ranging from 2 to 5. Depending on the partial pressures of the ethanol, anunonia and hydrogen feeds, different ethylamine selectivities were obtained. The degree of amine substitution was decreased (i.e. increasing MEA and decreasing DEA and TEA selectivities) by increasing the anunonia partial pressure or by decreasing either the ethanol or hydrogen partial pressures. At a reaction temperature of 180 · C, a WHSV of 2 gEtoH/ gcat h and an EtO H : NH3 : H2 : N2 molar feed ratio of 1 : 2 : 4.1 : 13.6, the steady state ethanol conversion activity was seen to decrease from 41 to 22 to 5 mol% as the metal was changed from nickel to cobalt to copper. These differences were caused largely by changes in metallic dispersion and metal reducibility, with the overall metallic surface area decreasing in the same order. When the specific activity of the catalysts was calculated, it was seen that the turnover frequency decreased from 0.11 to 0.09 to 0.05 molecules of ethanol per active site per second as the metal was changed from cobalt to nickel to copper. On this basis, it was concluded that principally cobalt is the best catalyst for the reductive amination reaction. The rate of ethylamine formation during reductive amination was modelled using Langmuir­ Hinshelwood kineticsUniversity since power rate law of models Cape proved inadequate Town in describing the behaviour of the cobalt, nickel and copper catalysts. Although previous kinetic studies indicated that the rate of alcohol dehydrogenation was the rate limiting step during reductive amination [Kryukov et al, 1967; Baiker et al, 1983], this was not observed for the silica supported cobalt, nickel and copper catalysts. In the case of the Co/Si02 catalyst, the rate determining step for the formation of MEA was described by the rate of surface reaction between ethanol and anunonia whereas the rates of DEA and TEA formation could be described by kinetic expressions formulated for a case in which the rate of ethanol adsorption was the controlling step. It was also found that the cobalt catalyst was partially deactivated Synopsis iii during amination due to the formation of cobalt nitride. The formation of cobalt nitride increased with increasing ammonia partial pressure but decreased with increasing hydrogen partial pressure. The formation of cobalt nitride was only significant below hydrogen to ammonia molar ratios of 2.5 : 1 however and in order to obtain maximum catalyst utilization, it is recommended that cobalt catalysts are operated at higher hydrogen to ammonia molar ratios. With Ni/Si02, the rates of MEA, DEA and TEA formation could be described using kinetic expressions formulated for a case where the rate of surface reaction was the controlling step. In order to obtain a good prediction of the experimental behaviour of the nickel catalyst, the kinetic expression describing the rate of MEA formation had to be modified by decreasing the power on the adsorption term from 2 to 1. This would indicate that MEA is formed via an Eley-Rideal mechanism over nickel catalysts where a gas phase molecule reacts with an adsorbed surface species. This mechanism was not supported by the other experimental evidence and it is possible that the assumed series reaction mechanism was too simple. As with the cobalt catalyst, the amination behaviour of the nickel catalyst could not be described by expressions developed for a case in which the rate of alcohol dehydrogenation was the rate limiting step. For the Cu/Si02 catalyst, the rates of MEA and DEA formation were best described by kinetic expressions derived for a case in which the rate controlling step was that of ethanol adsorption whereas the rate of TEA formation was best described by a kinetic expression in which the reaction between adsorbed ethanol and DEA was the controlling step. As a consequence of the seriesUniversity nature of the amination of reactionCape and the Town low MEA selectivities obtained using this metal, it was found that the rates of MEA and DEA formation were almost identical within the range investigated. The differences in ethylamine selectivity were ascribed to the difference in the strengths of adsorption (as estimated from the kinetic regressions) of ethanol and ammonia on the three metals. Depending on the relative surface concentrations of ethanol and ammonia, different degrees of amine substitution were obtained. The decrease in the NH3 : EtOH surface Synopsis iv concentration as the metal was changed from nickel to cobalt to copper results in a decrease in the specific MEA selectivity and an increase in the specific selectivity to DEA and TEA. Since cobalt was found to show the greatest specific activity for ethanol conversion during the reductive amination of ethanol using ammonia, the influence of a variety of parameters during catalyst preparation and activation on the catalytic performance were evaluated. It was seen that changing the preparation and activation procedures of a series of cobalt catalysts resulted in considerable changes to both the activity and the selectivity of the catalysts. The changes in activity were directly related to the reduced metallic surface area of the catalysts indicating that cobalt is the active catalytic component The changes in metallic surface area were due to changes in the metallic dispersion and changes in the reducibility of the supported cobalt The changes in metallic dispersion were largely due to thermal effects (i.e. the time and temperature of the calcination/reduction procedure) however significant changes in metallic dispersion were also obtained by changing the type of support which indicates that the chemical interaction between the metal precursor and the carrier metal is important Changes in metal reducibility were caused by the formation of difficult to reduce cobalt­ support species, the amount of which depended strongly on the chemical composition of the carrier materiaL The extent of reduction of cobalt catalysts decreased from 42 to 40 to 32 to 8 % as the aluminium content of the carrier material was increased from 0 to 4 to 13 to 100 wt%. The high extent of reduction of the Si02 supported cobalt catalyst coupled with a relatively high dispersion (8 %) resulted in this catalyst having the greatest activity. At a temperature of 180"C, a space velocity of 1 gEtoH/gcat·h and an EtOH : NH3 : H2 : N2 molar ratio of 1 : 2 : 8.6 : 17.6, the ethanol conversion of the Co/Si02 catalyst was 66 %. In contrast, the magnesiaUniversity supported cobalt catalyst of showedCape a conversion Town of less than 2 % at identical reaction conditions due to the very low extent of metal reduction on this catalyst Considerable differences in the specific ethylamine selectivity (i.e. the selectivity at the same reactant conversion) were also obtained upon changing the type of catalyst preparation and activation procedure. It was shown that the specific MEA selectivity decreased from 67 to 43%, the specific DEA selectivity increased from 30 to 50% and the specific TEA selectivity increased from 3 to 7% as the metal surface area of the catalyst was increased from 0.55 to Synopsis v 1.3 m2/gcat· Since the specific activity for the conversion of ethanol was not affected by the metal surface area, it could be deduced that the specific rate of ammonia consumption decreased with increasing metallic surface area.
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