Dynamic models of a reactive distillation column have been developed and implemented in this work. A model describing the steady state behavior of the system has been built in a first step. The results from this steady state model have been compared to data provided from an industrial collaborator and the reconciled model formed the basis for the development of a dynamic model. Four controlled and four manipulated variables have been determined in a subsequent step and step tests for the manipulated variables were simulated. The data generated by the step responses was used for fitting transfer functions between the manipulated and the controlled variables. RGA analysis was performed to find the optimal pairing for controller design. Feedback controllers of PID type were designed between the paired variables found from RGA and the controllers were implemented on the column model. Both servo and regulatory problems have been considered and tested.

The results of kinetic isotope determination and computational studies on Noyori-type catalytic systems for the hydrogenation of ketones are presented. The catalysts examined include RuH2(NHCMe2CMe2NH2)(R-binap) and RuH(NHCMe2CMe2NH2)(PPh3)2. These complexes are active catalysts for ketone hydrogenation in benzene without addition of an external base. The kinetic isotope effect (KIE) for catalysis by RuH2(NHCMe2CMe2NH2)(R-binap) was determined to be 2.0 ± (0.1). The calculated KIE for the model system RuH(NHCH2CH2NH2)(PH3)2 was 1.3, which is smaller than the experimentally observed value but does not include tunneling effects. The complex OsH(NHCMe2CMe2NH2)(PPh3)2 is known to display autocatalytic behaviour when it catalyzes the hydrogenation of acetophenone in benzene. Pseudo first-order reaction conditions are obtained via addition of the product alcohol at the beginning of each kinetic experiment. The KIE determined using various combinations of deuterium-labeled gas, alcohol and ketone was found to be 1.1 ± (0.2). DFT calculations were used to explore the effect of the alcohol and the KIE. An induction period is observed at the start of the hydrogenation that is attributed to the formation of an alkoxide complex. A novel, diamine-orchestrated hydrogen-bonding network is proposed based on DFT calculations to explain how the alkoxide is converted back to the active catalyst. The tetradentate complexes trans-RuHCl[PPh2(ortho-C6H4)CH2NHCH2)]2 and RuHCl[PPh2(ortho-C6H4)CH2NHCMe2)]2 are known to be catalysts for the hydrogenation of acetophenone and benzonitrile in toluene when activated by KOtBu/KH. DFT studies were performed and a mechanism is proposed. The calculated rate limiting step for acetone hydrogenation was found to be heterolytic splitting of dihydrogen, which agrees well with experiment. The novel outer-sphere sequential hydrogenation of a CN triple bond and then a C=N double bond is proposed. A mechanism is proposed, which is supported by DFT studies, to explain the selectivity observed in the nucleophilic attack of amines or aziridines on palladium -prenyl phosphines complexes. Calculations on based on a palladium complex with two phosphorus donor ligands indicated that the observed selectivity would not be produced. Using two new model intermediates with either THF or aziridine substituted for a phosphine ligand trans to the unhindered side of the prenyl ligand did predict the experimentally observed selectivity.

Several new late transition metal complexes containing P-O and P-N ligands derived from 2-dicyclohexylphosphinoacetaldehyde were synthesized. A facile one-pot template method is used for the synthesis of P-N complexes, where the phosphine aldehyde and amine can undergo a condensation reaction to form a phosphine-imine metal complex in the presence of a metal precursor. Metal complexes with phosphino-enolate, imine, and oxime ligands are synthesized. Ni(II), Pt(II), Rh(I) and Ir(I) metal centres were investigated. The Rh(I) and Ir(I) complexes contain a 1,5-cyclooctadiene ligand, thus resembling Crabtree’s hydrogenation catalyst [Ir(COD)(py)(PCy3)][PF6]. These complexes are also active catalysts for olefin hydrogenation. Furthermore, the synthesis of a new chiral amine functionalized NHC ligand is explored, which has potential applications as a ligand in the metal-catalyzed enantioselective hydrogenation of polar bonds. This ligand is inspired by previous achiral hydrogenation catalysts reported by Morris et al. that displayed high activity for a variety of unsaturated substrates.

A versatile method for the reduction of 2-pyrazolines was developed in this research. In every reduction attempt, aluminum trihydride successfully reduced the carbonnitrogen double bond. Since carbon-carbon double bonds were stable to aluminum trihydride, the preparation of 3-vinyl1-pyrazolines by a new synthetic route became possible. Using this method, 3,3-dimethyl-5-(1-isobutenyl)-1-pyrazoline was prepared. This compound was thermalytically decomposed, and the products of the decomposition were determined.In the course of this research, a one-step method for the preparation of cyclopropanes in high yield from 2pyrazolines was uncovered, but not fully developed. A new route to alpha-gamma-diamino compounds was also accomplished with the use of aluminum trihydride.Ball State UniversityMuncie, IN 47306

The results of kinetic isotope determination and computational studies on Noyori-type catalytic systems for the hydrogenation of ketones are presented. The catalysts examined include RuH2(NHCMe2CMe2NH2)(R-binap) and RuH(NHCMe2CMe2NH2)(PPh3)2. These complexes are active catalysts for ketone hydrogenation in benzene without addition of an external base. The kinetic isotope effect (KIE) for catalysis by RuH2(NHCMe2CMe2NH2)(R-binap) was determined to be 2.0 ± (0.1). The calculated KIE for the model system RuH(NHCH2CH2NH2)(PH3)2 was 1.3, which is smaller than the experimentally observed value but does not include tunneling effects. The complex OsH(NHCMe2CMe2NH2)(PPh3)2 is known to display autocatalytic behaviour when it catalyzes the hydrogenation of acetophenone in benzene. Pseudo first-order reaction conditions are obtained via addition of the product alcohol at the beginning of each kinetic experiment. The KIE determined using various combinations of deuterium-labeled gas, alcohol and ketone was found to be 1.1 ± (0.2). DFT calculations were used to explore the effect of the alcohol and the KIE. An induction period is observed at the start of the hydrogenation that is attributed to the formation of an alkoxide complex. A novel, diamine-orchestrated hydrogen-bonding network is proposed based on DFT calculations to explain how the alkoxide is converted back to the active catalyst. The tetradentate complexes trans-RuHCl[PPh2(ortho-C6H4)CH2NHCH2)]2 and RuHCl[PPh2(ortho-C6H4)CH2NHCMe2)]2 are known to be catalysts for the hydrogenation of acetophenone and benzonitrile in toluene when activated by KOtBu/KH. DFT studies were performed and a mechanism is proposed. The calculated rate limiting step for acetone hydrogenation was found to be heterolytic splitting of dihydrogen, which agrees well with experiment. The novel outer-sphere sequential hydrogenation of a CN triple bond and then a C=N double bond is proposed. A mechanism is proposed, which is supported by DFT studies, to explain the selectivity observed in the nucleophilic attack of amines or aziridines on palladium -prenyl phosphines complexes. Calculations on based on a palladium complex with two phosphorus donor ligands indicated that the observed selectivity would not be produced. Using two new model intermediates with either THF or aziridine substituted for a phosphine ligand trans to the unhindered side of the prenyl ligand did predict the experimentally observed selectivity.

Hydrogenated nitrile butadiene rubber (HNBR) which is known for its excellent elastomeric properties and mechanical retention properties after long time exposure to heat, oil and air is produced by the catalytic hydrogenation of nitrile butadiene rubber (NBR). Hydrogenation of NBR is carried out preferably in solution via homogeneous catalysis. As yet, it is being commercially produced in a semi-batch process where gaseous hydrogen continuously flows into a batch of reactant polymer. Several catalysts have been exploited successfully for the hydrogenation of NBR in organic solvents, which include palladium, rhodium, ruthenium, iridium and osmium complexes. Owing to the drawbacks of batch production (such as time taken for charging and discharging the reactants/products, heating and cooling, reactor clean up), and the huge demand for HNBR, a continuous process is proposed where potential time saving is possible in addition to the high turn over of the product. Numerical investigation of the HNBR production in a plug flow reactor and a continuous stirred tank reactor showed that a reactor with plug flow behavior would be economical and efficient. A static mixer (SM) reactor with open-curve blade internal geometry is designed based on the simulation and hydrodynamic results. The SM reactor was designed with 24 mixing elements, 3.81 cm ID and 90 cm length. The reactor has a jacket in which steam is used to heat the polymer solution. The hydrodynamics in the SM reactor (open-flat blade structure) with air-water system showed that plug flow could be achieved even under laminar flow conditions (Reh < 20). For a constant mean residence time, the Peclet number was varying such that it is 4.7 times the number of mixing elements (ne) used in the SM reactor. Empirical correlations were developed for gas hold up (εG) and overall mass transfer coefficient (KLa). The mass transfer experiments showed that high KLa, 4 to 6 times compared to that of the conventional reactors could be achieved in the SM reactor at particular operating conditions. Very important information on the Peclet number, liquid hold were obtained from the hydrodynamic experiments conducted with the actual working fluids (hydrogen, polymer solutions) in the SM reactor. The superficial gas velocity had an adverse effect on both Peclet number and liquid hold up. The viscosity of the polymer solution also had a marginal negative effect on the Peclet number while a positive effect on the liquid hold up. The hydrogenation performance with the homogeneous catalyst OsHCl(CO)(O2)(PCy3)2 was performed in the continuous process with SM reactor. Complete hydrogenation of NBR was possible in a single pass. The effect of mean residence time, catalyst and polymer concentration on the final degree of hydrogenation was studied. The minimum catalyst required to achieve degree of hydrogenation over 97% was empirically found and an empirical correlation was developed for degree of hydrogenation as a function of operating conditions and parameters. Hydrogenation in the SM reactor is modeled by using plug flow with axial dispersion model that is coupled with the concentrations of carbon-carbon double bond, hydrogen and osmium catalyst. The model involves coupled, non-linear partial differential equations with different dimensionless parameters. The proposed model was verified with the experimental results obtained from the hydrogenation and hydrodynamic experiments. The model could satisfactorily predict the degree of hydrogenation obtained from experimental results at various operating conditions. In general, the designed continuous process with SM reactor performed well and was an effective method of manufacturing HNBR on a continuous basis. The designed system is amicable to the industrial operating conditions and promises to be highly efficient and economic process for production of HNBR.

Hydrogenated nitrile butadiene rubber (HNBR) which is known for its excellent elastomeric properties and mechanical retention properties after long time exposure to heat, oil and air is produced by the catalytic hydrogenation of nitrile butadiene rubber (NBR). Hydrogenation of NBR is carried out preferably in solution via homogeneous catalysis. As yet, it is being commercially produced in a semi-batch process where gaseous hydrogen continuously flows into a batch of reactant polymer. Several catalysts have been exploited successfully for the hydrogenation of NBR in organic solvents, which include palladium, rhodium, ruthenium, iridium and osmium complexes. Owing to the drawbacks of batch production (such as time taken for charging and discharging the reactants/products, heating and cooling, reactor clean up), and the huge demand for HNBR, a continuous process is proposed where potential time saving is possible in addition to the high turn over of the product. Numerical investigation of the HNBR production in a plug flow reactor and a continuous stirred tank reactor showed that a reactor with plug flow behavior would be economical and efficient. A static mixer (SM) reactor with open-curve blade internal geometry is designed based on the simulation and hydrodynamic results. The SM reactor was designed with 24 mixing elements, 3.81 cm ID and 90 cm length. The reactor has a jacket in which steam is used to heat the polymer solution. The hydrodynamics in the SM reactor (open-flat blade structure) with air-water system showed that plug flow could be achieved even under laminar flow conditions (Reh < 20). For a constant mean residence time, the Peclet number was varying such that it is 4.7 times the number of mixing elements (ne) used in the SM reactor. Empirical correlations were developed for gas hold up (εG) and overall mass transfer coefficient (KLa). The mass transfer experiments showed that high KLa, 4 to 6 times compared to that of the conventional reactors could be achieved in the SM reactor at particular operating conditions. Very important information on the Peclet number, liquid hold were obtained from the hydrodynamic experiments conducted with the actual working fluids (hydrogen, polymer solutions) in the SM reactor. The superficial gas velocity had an adverse effect on both Peclet number and liquid hold up. The viscosity of the polymer solution also had a marginal negative effect on the Peclet number while a positive effect on the liquid hold up. The hydrogenation performance with the homogeneous catalyst OsHCl(CO)(O2)(PCy3)2 was performed in the continuous process with SM reactor. Complete hydrogenation of NBR was possible in a single pass. The effect of mean residence time, catalyst and polymer concentration on the final degree of hydrogenation was studied. The minimum catalyst required to achieve degree of hydrogenation over 97% was empirically found and an empirical correlation was developed for degree of hydrogenation as a function of operating conditions and parameters. Hydrogenation in the SM reactor is modeled by using plug flow with axial dispersion model that is coupled with the concentrations of carbon-carbon double bond, hydrogen and osmium catalyst. The model involves coupled, non-linear partial differential equations with different dimensionless parameters. The proposed model was verified with the experimental results obtained from the hydrogenation and hydrodynamic experiments. The model could satisfactorily predict the degree of hydrogenation obtained from experimental results at various operating conditions. In general, the designed continuous process with SM reactor performed well and was an effective method of manufacturing HNBR on a continuous basis. The designed system is amicable to the industrial operating conditions and promises to be highly efficient and economic process for production of HNBR.

A novel catalytic process for producing high-purity, elevated-pressure hydrogen from synthesis gas was proposed and investigated. The process combines the advantages of low investment and operating costs with the flexibility to adapt to a small-scale operation. The process consists of a loop containing two complementary reactions: ethanol dehydrogenation and acetaldehyde hydrogenation. In one part of the loop, hydrogen is produced by dehydrogenation of ethanol to acetaldehyde. Since acetaldehyde is a liquid under standard conditions, it can be easily separated and pure hydrogen is obtained. In the other part of the loop, hydrogen contained in synthesis gas is reacted with acetaldehyde to produce ethanol and purified carbon monoxide. Ethanol, also a liquid under standard conditions, is easily removed and purified carbon monoxide is obtained, which can be further water-gas shifted to produce more hydrogen. Various dimensionless criteria were evaluated to confirm there was no significant effect of heat and mass transfer limitations and thus the experimental results represent true kinetics. Furthermore, a thermodynamic study was conducted using a Gibbs free energy minimization model to identify the effect of reaction conditions on ethanol/acetaldehyde conversion and determine the thermodynamically favourable operating conditions. Various catalysts were synthesized, characterized and screened for each reaction in a down-flow, fixed-bed quartz reactor. A novel gas chromatography analysis method allowing for an on-line detection of all products was also developed. Unsupported copper in the form of copper foam and copper supported on three different high surface supports were evaluated in ethanol dehydrogenation. Copper foam provided the lowest activity, because of its low surface area. Cu/SiO2 was the most active catalyst for ethanol dehydrogenation. The effects of temperature, pressure, residence time, and feed composition on ethanol conversion and product composition were determined. While increasing temperature or residence time resulted in increased ethanol conversion, elevated pressure and water content in the feed had no effect on ethanol conversion. On the other hand, acetaldehyde selectivity decreased with increasing temperature, pressure and residence time, as acetaldehyde participated in undesirable transformations to secondary products, out of which the most dominant was ethyl acetate. The maximum operating temperature was limited by the stability of the copper catalyst, which deactivated by sintering at temperatures higher than 300°C. The range of temperatures investigated was from 200°C to 350°C, while pressures ranged from atmospheric to 0.5 MPa. For ethanol:water ratios <1, the addition of water to the ethanol feed improved the catalyst stability and acetaldehyde selectivity, but a detrimental effect was observed at higher ratios. The introduction of acetaldehyde into the feed always lowered the conversion, thus indicating a need for stream purification within the loop. An empirical kinetic model was used to determine the activation energy, the order of reaction and the frequency factor. Unsupported and SiO2-supported copper catalysts were compared in acetaldehyde hydrogenation. Pure copper was identified as the best catalyst. Effects of temperature, pressure, residence time, feed composition and catalyst promoter on acetaldehyde conversion and product composition were evaluated. The acetaldehyde hydrogenation was enhanced by increased temperature, pressure and residence time and suppressed in presence of Fe or Zn promoters. Once again, at elevated temperature and residence time, ethanol combined with acetaldehyde to produce undesired ethyl acetate. CO acted as an inert when testing with the pure copper catalyst, but slightly decreased conversion with the supported catalyst. A decrease in conversion was also observed with the introduction of water and ethanol in the feed, once again indicating a requirement for feed purity within the loop. A temperature range of 150-300°C was investigated with catalysts deactivating at temperatures exceeding 250°C. A pressure range identical to ethanol dehydrogenation was used: 0.1-0.5 MPa. Again, an empirical kinetic model allowed determination of the activation energy, the order of reaction and the frequency factor.

A novel catalytic process for producing high-purity, elevated-pressure hydrogen from synthesis gas was proposed and investigated. The process combines the advantages of low investment and operating costs with the flexibility to adapt to a small-scale operation. The process consists of a loop containing two complementary reactions: ethanol dehydrogenation and acetaldehyde hydrogenation. In one part of the loop, hydrogen is produced by dehydrogenation of ethanol to acetaldehyde. Since acetaldehyde is a liquid under standard conditions, it can be easily separated and pure hydrogen is obtained. In the other part of the loop, hydrogen contained in synthesis gas is reacted with acetaldehyde to produce ethanol and purified carbon monoxide. Ethanol, also a liquid under standard conditions, is easily removed and purified carbon monoxide is obtained, which can be further water-gas shifted to produce more hydrogen. Various dimensionless criteria were evaluated to confirm there was no significant effect of heat and mass transfer limitations and thus the experimental results represent true kinetics. Furthermore, a thermodynamic study was conducted using a Gibbs free energy minimization model to identify the effect of reaction conditions on ethanol/acetaldehyde conversion and determine the thermodynamically favourable operating conditions. Various catalysts were synthesized, characterized and screened for each reaction in a down-flow, fixed-bed quartz reactor. A novel gas chromatography analysis method allowing for an on-line detection of all products was also developed. Unsupported copper in the form of copper foam and copper supported on three different high surface supports were evaluated in ethanol dehydrogenation. Copper foam provided the lowest activity, because of its low surface area. Cu/SiO2 was the most active catalyst for ethanol dehydrogenation. The effects of temperature, pressure, residence time, and feed composition on ethanol conversion and product composition were determined. While increasing temperature or residence time resulted in increased ethanol conversion, elevated pressure and water content in the feed had no effect on ethanol conversion. On the other hand, acetaldehyde selectivity decreased with increasing temperature, pressure and residence time, as acetaldehyde participated in undesirable transformations to secondary products, out of which the most dominant was ethyl acetate. The maximum operating temperature was limited by the stability of the copper catalyst, which deactivated by sintering at temperatures higher than 300°C. The range of temperatures investigated was from 200°C to 350°C, while pressures ranged from atmospheric to 0.5 MPa. For ethanol:water ratios <1, the addition of water to the ethanol feed improved the catalyst stability and acetaldehyde selectivity, but a detrimental effect was observed at higher ratios. The introduction of acetaldehyde into the feed always lowered the conversion, thus indicating a need for stream purification within the loop. An empirical kinetic model was used to determine the activation energy, the order of reaction and the frequency factor. Unsupported and SiO2-supported copper catalysts were compared in acetaldehyde hydrogenation. Pure copper was identified as the best catalyst. Effects of temperature, pressure, residence time, feed composition and catalyst promoter on acetaldehyde conversion and product composition were evaluated. The acetaldehyde hydrogenation was enhanced by increased temperature, pressure and residence time and suppressed in presence of Fe or Zn promoters. Once again, at elevated temperature and residence time, ethanol combined with acetaldehyde to produce undesired ethyl acetate. CO acted as an inert when testing with the pure copper catalyst, but slightly decreased conversion with the supported catalyst. A decrease in conversion was also observed with the introduction of water and ethanol in the feed, once again indicating a requirement for feed purity within the loop. A temperature range of 150-300°C was investigated with catalysts deactivating at temperatures exceeding 250°C. A pressure range identical to ethanol dehydrogenation was used: 0.1-0.5 MPa. Again, an empirical kinetic model allowed determination of the activation energy, the order of reaction and the frequency factor.

In this study, we took four diamines of different carbon chain lengthes to synthesize several thiosalen derived zinc(II) complexes, i.e. N, N¡¦-Bis- (2-thio-benzylidene)- 1,3-propylenediaminato-zinc(II)(1),N,N¡¦-Bis(2-thio-benzylidene)-2,2-dimethyl- 1,3-propylenediaminato-zinc(II)(2),N,N¡¦-Bis-(2-thio-benzylidene)-1,2-ethylene- diaminato-zinc(II)(3),andN,N¡¦-Bis(2-thio-benzylidene)-1-methyl-1,2-ethylene- diaminato-zinc(II)(4). The crystal structure of 1 was shown to be trimeric. We then used NaBH4 to reduced complexes1, 2, and 4 to get complexes 5, 6, and 7 respectively for reactivity and structure studies. To expand our current study, we also synthesized nickel analogue (8) of complex 1 by transmetallation.