Equilibrium swelling measurements of network and semicrystalline polymers in supercritical carbon dioxide using high-pressure NMR

The extent of swelling of cross-linked poly(dimethylsiloxane) and linear low-density poly(ethylene) in supercritical CO2 has been investigated using high-pressure NMR spectroscopy and microscopy. Poly(dimethylsiloxane) was cross-linked to four different cross-link densities and swollen in supercritical CO2. The Flory-Huggins interaction parameter, x, was found to be 0.62 at 300 bar and 45 degrees C, indicating that supercritical CO2 is a relatively poor solvent compared to toluene or benzene. Linear low-density poly(ethylene) was shown to exhibit negligible swelling upon exposure to supercritical CO2 up to 300 bar. The effect Of CO2 pressure on the amorphous region of the poly(ethylene) was investigated by observing changes in the H-1 T-2 relaxation times of the polymer. These relaxation times decreased with increasing pressure, which was attributed to a decrease in mobility of the polymer chains as a result of compressive pressure.

Comparisons of the structural and catalytic properties of Ti-HMS synthesized using the hydrothermal and molecular designed dispersion methods

Titanium containing wormhole-like mesoporous silicas, denoted Ti-HMS, synthesized both via the hydrothermal synthesis route and the post synthesis grafting technique, known as molecular designed dispersion, have been successfully applied in the gas phase oxidation of Toluene to CO and CO2. Selectivity towards CO2 for all catalysts, at temperatures between 400-600degreesC, was above 80%. Benzene and benzaldehyde were observed at temperatures above 450degreesC, but in very low concentrations. The conversion of toluene was shown to increase significantly when the V-TEX/N-MESO ratios were increased from 0.07 to 0.84. No significant difference in catalytic activity was observed for catalysts prepared via the different synthesis techniques. The catalytic activity also depends on the concentration of tetrahedrally coordinated titanium atoms and not on the total concentration of titanium in the catalyst.

Oxidation of organic compounds in molten salts

The objective of this research was to investigate the oxidation of organic compounds in molten alkali metal hydroxides containing manganates. It has been shown that controlled oxidation can be readily achieved with high specificity to give products in high yield with very short reaction times. The concurrent changes in the melt were monitored using a vibrating platinum indicator electrode with a quazi-reference electrode which was successfully developed for use in molten (Na-K)OH eutectic at 523K. Henry's Law constants for water in the molten eutectic system (Na-K)OH have been measured and used to calculate the water concentration in the melt. The electrochemistry of manganates in molten (Na-K)OH eutectic at 523K has been studied using the vibrating platinum electrode, and the existence of the species Mn(II), Mn(II!), Mn(IV), Mn(V) and Mn(VI) in such melts has been investigated at various water concentrations. The half-wave potentials of the voltammetric waves were measured versus the cathodic limit of the melt. The stability of Mn(V) or Mn(VI) in the melt was achieved by varying the water concentration. A range of organic chemicals has been passed through molten (Na-K)OH at 523K and the reactions of these chemicals with the melt have been studied. The same organics were then passed through molten (Na-K)OH containing stabilized Mn(V) or Mn{VI) without violent reaction. Methanol, allyl alcohol, propane 1, 2 diol, I-heptene and acetone were oxidized by Mn(V) and Mn(VI). Ethanol was only oxidized by Mn(VI), isopropanol and benzyl alcohol were only oxidized by Mn(V). Npropanol, butanol, 2 methyl propan-2-ol, n-hexane, n-heptane toluene and cyclohexane were unchanged by both Mn(V) and Mn(VI). Detailed experiments have been performed on the reactions of ethanol, iso-propanol and methanol in molten (Na-K)OH containing stabilized Mrt(V) or Mn(VI), and reaction mechanisms have been postulated. Ethanol and iso-propanol were oxidized to acetaldehyde and acetone respectively with a potential for useful chemical process. The oxidation of methanol could be developed as a basis for an industrial methanol disposal process.

Advanced liquid-liquid extraction : studies in a laboratory mixer-settler

A ten stage laboratory mixer-settler has been designed, constructed and operated with efficiencies up to 90%. The phase equilibrium data of the system acetic acid-toluene-water at different temperatures has been determined and correlated. Trials for prediction of these data have been investigated and a good agreement between the experimental data and the predictions obtained by the NRTL equation have been found. Extraction processes have been analysed. A model for determination of the time needed for a countercurrent stage-wise process to come to steady state has been derived. The experimental data was in reasonable agreement with this model. The discrete maximum principle has been applied to optimize the countercurrent extraction process and proved to be highly successful in predicting the optimum operating conditions which were confirmed by the experimental results. The temperature has proved to be a prosolvent for mass transfer in both directions but the temperature profile functioned as an anti solvent.

Coalescence of secondary dispersions in fibrous beds

SUMMARY A study has been made of the coalescence of secondary dispersions in a fibrous bed. The literature pertaining to the formation, hydrodynamic behaviour and methods of separation of droplets less than one hundred micrometres in diameter has been reviewed with particular reference to fibrous bed coalescers. The main operating parameters were identified as inlet drop size distribution, phase ratio, superficial velocity and the thickness and voidage of the bed . A recirculatory rig with interchangeable fibrous bed pads was designed and operated with toluene-water dispersions generated by a combination of centrifugal pumps . Inlet drop sizes were analysed using a Coulter Counter and outlet drops were sized photographically. A novel technique, involving conductivity measur ements at different planes in the bed, was developed to measure hold up distribution. Single phase flow and two phase flow pressure drops were correlated by a Blake-Kozeny type equation. Exit drop size was independent of inlet drop size distribution and phase ratio but a function of superficialvelocity and packing thickness. Average bed hold up was independent of inlet drop size distribution and phase ratio, but decreased with increase in superficial velocity. Hold up was not evenly distributed in the bed, the highest value occurred at the inlet followed by a sharp -2 drop at approximately 1.2 x 10 m. Hold up remained constant throughout the rest of the bed until the exit plane, where it increased. From the results, a mechanism is postulated involving: (a) Capture of the inlet drops followed by interdrop coalescence until an equilibrium value is reached. (b) Equilibrium size droplets flowing as rivulets through the intermediate portion of the bed, and (c) Each rivulet forms droplets at the exit face, which detach by a 'drip point' mechanism.

Coalescence of secondary dispersions

A study has been made of the coalescence of secondary dispersions in beds of woven meshes. The variables investigated were superficial velocity, bed depth, mesh geometry and fibre material; the effects of presoaking the bed in the dispersed phase before operation were also considered. Equipment was design~d to generate a 0.1% phase ratio toluene in water dispersion whose mean drop size was determined using a Coulter Counter. The coalesced drops were sized by photography and a novel holographic technique was developed to evaluate the mean diameter of the effluent secondary drops. Previous models describing single phase flow in porous media are reviewed and it was found that the experimental data obtained in this study is best represented by Keller's equation which is based on a physical model similar to the internal structure of the meshes. Statistical analysis of two phase data produced a correlation, for each mesh tested, relating the pressure drop to superficial velocity and bed depth. The flow parameter evaluated from the single phase model is incorporated into a theoretical comparison of drop capture mechanisms which indicated that direct and indirect interception are predominant. The resulting equation for drop capture efficiericy is used to predict the initial, local drop capture rate in a coalescer. A mathematical description of the saturation profiles was formulated and verified by average saturation data. Based 6n the Blake-Kozeny equation, an expression is derived analytically to predict the two phase pressure drop using the parameters which characterise the saturation profiles. By specifying the local saturation at the inlet face for a given velocity, good agreement between experimental pressure drop data and the model predictions was obtained.

The design of a high pressure solvent extraction process using liquid ammonia as solvent

The literature on the potential use of liquid ammonia as a solvent for the extraction of aromatic hydrocarbons from mixtures with paraffins, and the application of reflux, has been reviewed. Reference is made to extractors suited to this application. A pilot scale extraction plant was designed comprising a Scm. diameter by 12Scm. high, 50 stage Rotating Disc Contactor with 2 external settlers. Provision was made for operation with, or without, reflux at a pressure of 10 bar and ambient temperature. The solvent recovery unit consisted of an evaporator, compressor and condenser in a refrigeration cycle. Two systems were selected for study, Cumene-n-Heptane-Ammonia and Toluene-Methylcyclohexane-Ammonia. Equlibrium data for the first system was determined experimentally in a specially-designed, equilibrium bomb. A technique was developed to withdraw samples under pressure for analysis by chromatography and titration. The extraction plant was commissioned with a kerosine-water system; detailed operating procedures were developed based on a Hazard and Operability Study. Experimental runs were carried out with both ternary ammonia systems. With the system Toluene-Methylcyclohexane-Ammonia the extraction plant and the solvent recovery facility, operated satisfactorily, and safely,in accordance with the operating procedures. Experimental data gave reasonable agreement with theory. Recommendations are made for further work with plant.

Studies in the anionic polymerization of methyl methacrylate

A study has been made of the anionic polymerization of methyl methacrylate using butyllithium and polystyryl lithium as initiators and using aluminium triisobutyl as a cocatalyst. The aspects of the polymerization that were examined were the effect of changing the order of addition of reagents, the temperature at which polymerization takes place and the polarity of the solvent. Trends were assessed in terms of molecular weight, molecular weight distribution and tacticity. In addition, a second monomer addition test was carried out to verify that the polymerization was truly a living one, and a kinetic study was attempted. Studies to investigate the effect of changing the order of addition of reagents showed that polymer with similar polydispersities and tacticities are produced whether the pre-mixing (mixing initiator and cocatalyst before addition of monomer) or the post-mixing (mixing monomer and cocatalyst before addition of initiator) method were used. However, polymerizations using the post-mixing mixing method demonstrated lower initiator efficiencies, possibly indicating a different initiating species. Investigations into the effect of changing the polymerization temperature show the molecular weight distribution to narrow as the temperature decreases, although a small amount of low molecular weight tailing was also observed at low temperature. A clear relationship between tacticity and temperature was observed with syndiotacticity increasing with decreasing temperature. Changes in solvent polarity were achieved by using mixtures of the standard solvent, toluene, with varying amounts of cyclohexane, tetrahydrofuran or dichloromethane. Experiments at low solvent polarity (using toluene/cyclohexane mixtures) showed problems with initiator solubility but produced polymer with lower polydispersity and higher syndiotacticity than in toluene alone. Experiments using toluene/THF mixtures yielded no polymer, thought to be owing to a side reaction between THF and aluminium triisobutyl. Increased solvent polarity, achieved using toluene/dichloromethane mixtures produced polymer with higher polydispersity and at lower yields than the conventional system, but also with higher syndiotacticity. Second monomer addition reactions demonstrated that the polymerization was 'living' since an increase in molecular weight was observed with no increase in polydispersity. Kinetic studies demonstrated the high speed of the polymerization but yielded no useful data.

The synthesis of biodegradable polymers using aluminium alkoxide initiators

Alkyl aluminium alkoxides have been used as initiators for the ring opening polymerisation of ε-caprolactone and δ-valerolactone. The effect of the reaction solvent on the kinetics of the polymerisation of ε-caprolactone has been studied. The rate of polymerisation was found to be faster in solvents of lower polarity and donor nature such as toluene. In general solvents of higher polarity resulted in a decreased rate of polymerisation. However solvents such as THF or DMF with a lone pair of electrons capable of forming a complex with the aluminium centre slowed the polymerisation further. The size of the monomer also proved to be an important factor in the kinetics of the reaction. The six membered ring, δ-valerolactone has less ring strain than the seven membered ring ε-caprolactone and thus the polymerisation of δ-valerolactone is slower than the corresponding polymerisation of ε-caprolactone. Both the alkoxide and alkyl group structures have an effect on the polymerisation. In general bulkier alkoxide groups provide greater steric hindrance around the active site at the beginning of the reaction. This causes an induction or a build up period that is related to the both the steric hindrance and also the electronic effects provided by the alkoxide group. The alkyl group structure has an effect throughout the polymerisation because it remains adjacent to the active centre. The number of alkoxide groups on the aluminium centre is also important, using a dialkoxide as an initiator yields polymers with molecular weights approximately half that of the corresponding reactions using a mono alkoxide. Transesterification reactions have also been found to occur after most of the monomer has been consumed. These transesterification reactions are exaggerated as temperature increases. A method of producing tri-block co-polymers has also been developed. A di-hydroxy functional pre-polymer, PHBV, was reacted with an aluminium alkyl to form a di-alkoxide macroinitiator which was subsequently used as an initiator for the polymerisation of ε-caprolactone to form an ABA type tri-block co-polymer. The molecular weight and other properties were predictable from the initial monomer/initiator ratios.

Synthesis and characterisation of vinyl block copolymers

A study has been made of the anionic polymerisation of methyl methacrylate using butyllithium and polystyryl lithium as initiators and the effects of lithium chloride and aluminium alkyls on the molecular weight and molecular weight distributions. Diblock copolymers of styrene-b-methyl methacrylate were synthesised at -78oC in THF in the presence of lithium chloride, and at ambient temperatures in toluene in the presence of aluminium alkyls. Studies in the presence of lithium chloride showed that the polymerisation was difficult to control; there was no conclusive evidence of a living system and the polydispersity indices were between 1.5 and 3. However, using relatively apolar solvents, in the presence of aluminium alkyls, homopolymerisation of methyl methacrylate showed characteristics of a living polymerisation. An investigation of the effects of the structures of the lithium and aluminium alkyls on the efficiency of initiation showed that a t-butyllithium/triisobutylaluminium initiating system exhibited an efficiency of 80%, compared with lower efficiencies (typically 30%) for systems based on butyllithium/triethylaluminium.The polydispersity index was found to decrease from ∼2.2 to ∼1.5 when butyllithium was replaced by t-butyllithium. The efficiency of the initiator was found to be solely dependent on the size of the alkyl group of the aluminium component, whereas the polydispersity index was found to be solely dependent on the size of the alkyl group on the lithium component. The aluminium alkyl is thought to be co-ordinated to the ester carbonyl groups of both the monomer and polymer. There is a critical degree of polymerisation, at which point the rate of polymerisation decreases, which probably relates to a change in structure of the active chain end. Characterisation of poly(styrene )-b-poly(4-vinylpyridine) and poly(styrene)-b-poly(4-vinylpyridine methyl iodide) diblock copolymers using static light scattering techniques, showed the formation of star-shaped 'reverse' micelles when placed in toluene. Temperature effects on micellization behaviour are only exhibited for the unquaternised micelles, which showed characterisically lower aggregation numbers than their quaternised counterparts. A suitable solvent was not obtained for characterisation of the styrene-b-methyl methacrylate diblock copolymers synthesized.

BTX extraction by sulfolane in a mixer-settler cascade

The literature relating to the extraction of the aromatics, benzene, toluene and xylene (BTX) using different commercial solvents, and to mixer-settler design and performance, has been reviewed. Liquid-liquid equilibria of the ternary systems: hexane-benzene-sulfolane, n-heptane-toluene-sulfolane, and octane-xylene-sulfolane were determined experimentally at temperatures of 30oC, 35oC, and 40oC. The work was then extended to a multicomponent system. The data were correlated by using Hand's method and were found to be in a good agreement with theoretical predictions using the UNIFAC method. A study was made of the performance of a 10-stage laboratory mixer-settler cascade for the extraction of BTX from a synthetic reformate utilizing sulfolane as a solvent. Murphree stage efficiency decreased with stage number but 99% extraction was achievable within 4 stages. The effects of temperature, phase ratio, and agitator speed were investigated. The efficiency increased with agitator speed but > 1050 rpm resulted in secondary haze formation. An optimum temperature of 30oC was selected from the phase equilibria; the optimum solvent: feed ratio was 3:1 for 4 stages. The experimental overall mass transfer coefficients were compared with those predicted from single drop correlations and were in all cases greater, by a factor of 1.5 to 3, due to the surface renewal associated with drop break-up and coalescence promoted by agitation. A similar investigation was performed using real reformate from the Kuwait Oil Company. The phase ratios were in the range 0.5 to 1 to 3.25 to 1, the agitator speed 1050 rpm, and the operating temperature 30oC. A maximum recovery of 99% aromatics was achieved in 4 stages at a phase ratio of 3.25 to 1. A backflow model was extended to simulate conditions in the mixer-settler cascade with this multicomponent system. Overall mass transfer coefficients were estimated by obtaining the best fit between experimental and predicted concentration profiles. They were up to 10% greater than those with the synthetic feed but close agreement was not possible because the distribution coefficient and phase ratio varied with stage number. Sulfolane was demonstrated to be an excellent solvent for BTX recovery and a mixer-settler cascade was concluded to be a technically viable alternative to agitated columns for this process.

The temperature dependence of the electro-optic kerr effect in solutions

A novel Kerr cell of greater optical path length and temperature stability has been designed and built. The Kerr effect experimental has been substantially automated using an Apple IIe computer. Software has been written allowing the computer to partially control the Kerr effect equipment and to acquire and analyse the relevant data.The temperature dependent electro-optic Kerr effect of 2-methyl-4-nitroaniline, p-nitroaniline, nitrobenzene, aniline, and toluene as solutions in 1, 4-dioxane has been studied. The Kerr effect measurements combined with dipole moment, depolarisation ratio, dielectric, and electronic polarisation measurements have been used to calculate the first hyperpolarisability of the solute.Although first hyperpolarisabilities for the compounds studied have been measured in various physical states using a variety of experimental techniques, it is gratifying to find that the values presented in this thesis have a linear relationship with values reported by other workers.

The use of enzyme catalysts in organic media for the synthesis of biodegradable polyesters

The enzyme catalysed polytransesterification of diesters with diols was investigated under various conditions. The most consistent results were obtained using crude porcine pancreatic lipase (PPL) suspended in anhydrous diethyl ether. Addition of molecular sieve to the above system gave higher molecular weight products. The PPL catalysed reaction of bis(2,2,2-trichlorethyl) adipate and glutarate with butane-1,4-diol in anhydrous ether with and without molecular sieve was investigated over a range of times from 8 to 240 hours. The 72 hour adipate reaction with molecular sieve gave the highest molecular weight polymer (Mn 6,500 and Mw 9,400). The glutarate gave the maximum molecular weight polyester after 24 hours (Mn 5,700 and Mw 9,500). Occasionally the glutarate reaction produced very high molecular weight polyester-enzyme complexes. Toluene generally gave lower molecular weight products than diethyl ether. Dichloromethane and tetrahydrofuran gave mainly dimers and trimers. Alternative enzyme and diol systems were also investigated. These yielded no polymeric products. The molecular weights of the polyesters were determined by 1H NMR end-group analysis and by GPC. The molecular weights determined by NMR were on average about twice as great as those determined by GPC. The synthesis of the following diesters is described: i)Bis(2,2,2-trichloroethyl) succinate, glutarate, adipate, trans-3-hexenedioate, and trans-3,4-epoxyadipate. ii) Diphenyl glutarate and adipate.iii)Bis(2,2,2-fluoroethyl) glutarate and trans-3-hexendioate.iv) Divinyl glutarate. v) N,N'Glutaryl dicyclohexanone oxime.The polytransesterification of all the above esters with diols was investigated. The easily synthesised bis(2,2,2-trichloroethyl) glutarate and adipate gave the best results and the work was concentrated on these two esters.

The hydrodynamic behaviour and mass transfer characteristics of single droplets in a pulsed sieve plate column

The literature relating to the performance of pulsed sieve plate liquid-liquid extraction columns and the relevant hydrodynamic phenomenon have been surveyed. Hydrodynamic behaviour and mass transfer characteristics of droplets in turbulent and non-turbulent conditions have also been reviewed. Hydrodynamic behaviour, i.e. terminal and characteristic velocity of droplets, droplet size and droplet breakup processes, and mass transfer characteristics of single droplets (d≤0.6 cm) were investigated under pulsed (mixer-settler & transitional regimes) and non-pulsed conditions in a 5.0 cm diameter, 100 cm high, pulsed sieve plate column with three different sieve plate types and variable plate spacing. The system used was toluene (displaced) - acetone - distilled water. Existing photographic techniques for following and recording the droplet behaviour, and for observing the parameters of the pulse and the pulse shape were further developed and improved. A unique illumination technique was developed by which a moving droplet could be photographed using cine or video photography with good contrast without using any dye. Droplet size from a given nozzle and droplet velocity for a given droplet diameter are reduced under pulsing condition, and it was noted that this effect is enhanced in the presence of sieve plate. The droplet breakup processes are well explained by reference to an impact-breakup mechanism. New correlations to predict droplet diameter based on this mechanism are given below.vskip 1.0cm or in dimensionless groups as follows:- (We)crit= 3.12 - 1.79 (Eo)crit A correlation based on the isotropic turbulence theory was developed to calculate droplet diameter in the emulsion regime.vskip 1.0cm Experimental results show that in the mixer-settler and transitional regimes, pulsing parameters had little effect on the overall dispersed phase mass transfer coefficient during the droplet formation and unhindered travel periods.

Coalescence of secondary dispersions in packed beds

A study has been made of the coalescence of secondary dispersions in beds of monosized glass ballotini. The variables investigated were superficial velocity, bed depth, ballotini size and dispersed phase concentration. Equipment was designed to generate a toluene ln water dispersion with phase ratios from 0.1 - 1.0 v/v % and whose mean drop size was determined using a Coulter Counter. The coalesced drops were sized by photography and the mean diameter of the effluent drops was determined using a Malvern Particle Size Analyser. Previous models describing single phase flow in porous media are reviewed and it was found that the experimental data obtained in this study is best represented by the Carman-Kozeny equations. Relative permeability correlations were used to predict the saturation profiles across the bed from measured two phase pressure drop data. Theoretical comparison of drop capture mechanisms indicated that direct and indirect interception are predominant. The total capture efficiency for the bed can also be evaluated using Spielman and Fitzpatrick's correlation.The resulting equation is used to predict the initial, local drop capture rate in a coalescer. A mathematical description of the saturation profiles is formulated and verified by the saturation profiles obtained by relative permeability. Based on the Carman-Kozeny equation, an expression is derived analytically to .predict the two phase pressure drop using the parameters which characterise the saturation profiles. By specifying the local saturation at the inlet face for a given velocity and phase ratio, good agreement between experimental pressure drop data and the model predictions was obtained. An attempt to predict the exit drop size has been made using an analogy for flow through non cylindrical channels.