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.

Wideband inhibition modulates the effect of onset asynchrony as a grouping cue

Onset asynchrony is arguably the most powerful grouping cue for the separation of temporally overlapping sounds (see Bregman 1990). A component that begins only 30–50 ms before the others makes a greatly reduced contribution to the timbre of a complex tone, or to the phonetic quality of a vowel (e.g. Darwin 1984). This effect of onset asynchrony does not necessarily imply a cognitive grouping process; instead it may result from peripheral adaptation in the response to the leading component in the few tens of milliseconds before the other components begin (e.g., Westerman and Smith 1984). However, two findings suggest that the effect of onset asynchrony cannot be explained entirely by peripheral adaptation. First, though the effect is smaller, the contribution of a component to the phonetic quality of a short-duration vowel is reduced when it ends after the other components (Darwin and Sutherland 1984; Roberts and Moore 1991).

Contralateral influences of wideband inhibition on the effect of onset asynchrony as a cue for auditory grouping

Onset asynchrony is an important cue for segregating sound mixtures. A harmonic of a vowel that begins before the other components contributes less to vowel quality. This asynchrony effect can be partly reversed by accompanying the leading portion of the harmonic with an octave-higher captor tone. The original interpretation was that the captor and leading portion formed a perceptual group, but it has recently been shown that the captor effect depends on neither a common onset time nor harmonic relations with the leading portion. Instead, it has been proposed that the captor effect depends on wideband inhibition in the central auditory system. Physiological evidence suggests that such inhibition occurs both within and across ears. Experiment 1 compared the efficacy of a pure-tone captor presented in the same or opposite ear to the vowel and leading harmonic. Contralateral presentation was at least as effective as ipsilateral presentation. Experiment 2 used multicomponent captors in a more comprehensive evaluation of harmonic influences on captor efficacy. Three captors with different fundamental frequencies were used, one of which formed a consecutive harmonic series with the leading harmonic. All captors were equally effective, irrespective of the harmonic relationship. These findings support and refine the inhibitory account. © 2007 Acoustical Society of America.

Wideband tuneable fibre Bragg grating filters

A fibre Bragg grating filter device, tunable over 45 nm, is reported. The device has a wavelength setting time below 1.5 ms and a maximum tuning speed of 21 nm/ns.

Simultaneous clock recovery and data regeneration using a nonlinear optical loop mirror as an all-optical mixer

High-speed optical clock recovery, demultiplexing and data regeneration will be integral parts of any future photonic network based on high bit-rate OTDM. Much research has been conducted on devices that perform these functions, however to date each process has been demonstrated independently. A very promising method of all-optical switching is that of a semiconductor optical amplifier-based nonlinear optical loop mirror (SOA-NOLM). This has various advantages compared with the standard fiber NOLM, most notably low switching power, compact size and stability. We use the SOA-NOLM as an all-optical mixer in a classical phase-locked loop arrangement to achieve optical clock recovery, while at the same time achieving data regeneration in a single compact device

Virtual Gires-Tournois etalons realized with phase-modulated wideband chirped fiber gratings

We propose and demonstrate novel virtual Gires–Tournois (GT) etalons based on fiber gratings. By introducing an additional phase modulation in wideband linearly chirped fiber Bragg gratings, we have successfully generated GT resonance with only one grating. This technique can simplify the fabrication procedure while retaining the normal advantages of distributed etalons, including their full compatibility with optical fiber, low insertion loss, and low cost. Such etalons can be used as dispersion compensation devices in optical transmission systems.

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.

Investigating viscous fluid flow in an internal mixer using computational fluid dynamics

This thesis presents an effective methodology for the generation of a simulation which can be used to increase the understanding of viscous fluid processing equipment and aid in their development, design and optimisation. The Hampden RAPRA Torque Rheometer internal batch twin rotor mixer has been simulated with a view to establishing model accuracies, limitations, practicalities and uses. As this research progressed, via the analyses several 'snap-shot' analysis of several rotor configurations using the commercial code Polyflow, it was evident that the model was of some worth and its predictions are in good agreement with the validation experiments, however, several major restrictions were identified. These included poor element form, high man-hour requirements for the construction of each geometry and the absence of the transient term in these models. All, or at least some, of these limitations apply to the numerous attempts to model internal mixes by other researchers and it was clear that there was no generally accepted methodology to provide a practical three-dimensional model which has been adequately validated. This research, unlike others, presents a full complex three-dimensional, transient, non-isothermal, generalised non-Newtonian simulation with wall slip which overcomes these limitations using unmatched ridding and sliding mesh technology adapted from CFX codes. This method yields good element form and, since only one geometry has to be constructed to represent the entire rotor cycle, is extremely beneficial for detailed flow field analysis when used in conjunction with user defined programmes and automatic geometry parameterisation (AGP), and improves accuracy for investigating equipment design and operation conditions. Model validation has been identified as an area which has been neglected by other researchers in this field, especially for time dependent geometries, and has been rigorously pursued in terms of qualitative and quantitative velocity vector analysis of the isothermal, full fill mixing of generalised non-Newtonian fluids, as well as torque comparison, with a relatively high degree of success. This indicates that CFD models of this type can be accurate and perhaps have not been validated to this extent previously because of the inherent difficulties arising from most real processes.

Characterisation of a cavity transfer mixer as a chemical reactor

This research project examined the feasibility of using a cavity transfer mixer (CTM) as a continuous reactor to perform reactions between either solid or liquid reagents and polymer melt; reactions which have previously been typically carried out in batch reactor systems. Equipment has been developed to allow uniform and reproducible introduction of reagents into the polymer melt. Reactions have also been performed using batch processing equipment to enable comparison with the performance of the CTM. It was concluded that: a) there are certain reactions which cannot be carried out in a CTM, but which can be performed in a batch system such as a mill or a sigma blade mixer. This was found to be the case for some neutralisation reactions where the product was quasi crosslinked. b) the reactions that can be carried out in a CTM are performed more efficiently in a CTM than on a batch process. For example, when monomers were to be grafted onto polymers, this was more safely and efficiently performed in the CTM than in a mill or a sigma blade mixer. Residence time distributions (RTDs) for three CTMs were studied in order to gain an insight into the effect of CTM geometry on RTD, polymer melt flow pattern and reactor performance. A mathematical model has been developed to predict the influence of process parameters on RTD and the results compared with experimentally observed trends. The comparison was good. A programme of research has been drawn up to form the basis of an industrially based sponsored development project of the CTM reactor. This work programme was successfully marketed to companies with commercial interest in modified rubber and plastics as an integral part of the research programme of this thesis and the sponsored research programme has paralleled the work reported here.

Wideband-tuneable, nanotube mode-locked, fibre laser

Ultrashort-pulse lasers with spectral tuning capability have widespread applications in fields such as spectroscopy, biomedical research and telecommunications1–3. Mode-locked fibre lasers are convenient and powerful sources of ultrashort pulses4, and the inclusion of a broadband saturable absorber as a passive optical switch inside the laser cavity may offer tuneability over a range of wavelengths5. Semiconductor saturable absorber mirrors are widely used in fibre lasers4–6, but their operating range is typically limited to a few tens of nanometres7,8, and their fabrication can be challenging in the 1.3–1.5 mm wavelength region used for optical communications9,10. Single-walled carbon nanotubes are excellent saturable absorbers because of their subpicosecond recovery time, low saturation intensity, polarization insensitivity, and mechanical and environmental robustness11–16. Here, we engineer a nanotube–polycarbonate film with a wide bandwidth (>300 nm) around 1.55 mm, and then use it to demonstrate a 2.4 ps Er31-doped fibre laser that is tuneable from 1,518 to 1,558 nm. In principle, different diameters and chiralities of nanotubes could be combined to enable compact, mode-locked fibre lasers that are tuneable over a much broader range of wavelengths than other systems.

Virtual Gires-Tournois etalons realized with phase-modulated wideband chirped fiber gratings

We propose and demonstrate novel virtual Gires-Tournois (GT) etalons based on fiber gratings. By introducing an additional phase modulation in wideband linearly chirped fiber Bragg gratings, we have successfully generated GT resonance with only one grating. This technique can simplify the fabrication procedure while retaining the normal advantages of distributed etalons, including their full compatibility with optical fiber, low insertion loss, and low cost. Such etalons can be used as dispersion compensation devices in optical transmission systems. © 2007 Optical Society of America.

Simultaneous clock recovery and data regeneration using a nonlinear optical loop mirror as an all-optical mixer

High-speed optical clock recovery, demultiplexing and data regeneration will be integral parts of any future photonic network based on high bit-rate OTDM. Much research has been conducted on devices that perform these functions, however to date each process has been demonstrated independently. A very promising method of all-optical switching is that of a semiconductor optical amplifier-based nonlinear optical loop mirror (SOA-NOLM). This has various advantages compared with the standard fiber NOLM, most notably low switching power, compact size and stability. We use the SOA-NOLM as an all-optical mixer in a classical phase-locked loop arrangement to achieve optical clock recovery, while at the same time achieving data regeneration in a single compact device

Photonic processing for wideband cancellation and spectral discrimination of RF signals

Photonic signal processing is used to implement common mode signal cancellation across a very wide bandwidth utilising phase modulation of radio frequency (RF) signals onto a narrow linewidth laser carrier. RF spectra were observed using narrow-band, tunable optical filtering using a scanning Fabry Perot etalon. Thus functions conventionally performed using digital signal processing techniques in the electronic domain have been replaced by analog techniques in the photonic domain. This technique was able to observe simultaneous cancellation of signals across a bandwidth of 1400 MHz, limited only by the free spectral range of the etalon. © 2013 David M. Benton.

Metallocene ethylene-1-octene copolymers:influence of comonomer content on thermo-mechanical, rheological, and thermo-oxidative behaviours before and after melt processing in an internal mixer

The influence of the comonomer content in a series of metallocene-based ethylene-1-octene copolymers (m-LLDPE) on thermo-mechanical, rheological, and thermo-oxidative behaviours during melt processing were examined using a range of characterisation techniques. The amount of branching was calculated from 13C NMR and studies using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) were employed to determine the effect of short chain branching (SCB, comonomer content) on thermal and mechanical characteristics of the polymer. The effect of melt processing at different temperatures on the thermo-oxidative behaviour of the polymers was investigated by examining the changes in rheological properties, using both melt flow and capillary rheometry, and the evolution of oxidation products during processing using infrared spectroscopy. The results show that the comonomer content and catalyst type greatly affect thermal, mechanical and oxidative behaviour of the polymers. For the metallocene polymer series, it was shown from both DSC and DMA that (i) crystallinity and melting temperatures decreased linearly with comonomer content, (ii) the intensity of the ß-transition increased, and (iii) the position of the tan δmax peak corresponding to the a-transition shifted to lower temperatures, with higher comonomer content. In contrast, a corresponding Ziegler polymer containing the same level of SCB as in one of the m-LLDPE polymers, showed different characteristics due to its more heterogeneous nature: higher elongational viscosity, and a double melting peak with broader intensity that occurred at higher temperature (from DSC endotherm) indicating a much broader short chain branch distribution. The thermo-oxidative behaviour of the polymers after melt processing was similarly influenced by the comonomer content. Rheological characteristics and changes in concentrations of carbonyl and the different unsaturated groups, particularly vinyl, vinylidene and trans-vinylene, during processing of m-LLDPE polymers, showed that polymers with lower levels of SCB gave rise to predominantly crosslinking reactions at all processing temperatures. By contrast, chain scission reactions at higher processing temperatures became more favoured in the higher comonomer-containing polymers. Compared to its metallocene analogue, the Ziegler polymer showed a much higher degree of crosslinking at all temperatures because of the high levels of vinyl unsaturation initially present.

Multifunctional, tunable and wideband all-fiber filter based on θ shaped microfiber resonator

A compact Θ shaped microfiber resonator for multifunctional, tunable and wideband filter is proposed. The filtering performance of reflection and transmission spectra depending on coupling coefficients and cavity length is theoretically investigated and experimentally demonstrated. © 2015 OSA.