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Three phase azeotropic distillationCairns, Brett P. January 1988 (has links)
Thesis (Ph. D.)--University of Sydney, 1989. / Includes copies of 5 published papers co-authored by Cairns. Bibliography: leaves 321-332. Also available in print form.
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Rapid screening of conceptual design alternatives for distillation processes /Brüggemann, Stefan. January 2005 (has links)
Zugl.: Aachen, Techn. Hochsch., Diss.
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Azeotropic behavior in the critical region: the system acetone--n-pentane /Cherry, Robert Homer January 1966 (has links)
No description available.
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Liquid-vapor phase behavior in the critical region in systems which form azeotropes : the binary systems perfluoro-n-heptane with n-alkanes /Jordan, Lawrence William January 1959 (has links)
No description available.
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Intermolecular forces in the critical azeotropic system propane-perfluorocyclobutane : description of forces in the vapor region via virial coefficients and in the liquid region via internal pressure and internal force /Barber, Jerry Randel January 1968 (has links)
No description available.
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A study of azeotropy and its effect on the critical region of binary systems : the perfluoro-methylcyclohexane -isomeric hexane systems /Genco, Joseph Michael January 1965 (has links)
No description available.
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Vapour-liquid-liquid equilibria measurements for the dehydration of low molecular weight alcohols via heterogeneous azeotropic distillationBrits, Leanne 03 1900 (has links)
Thesis (MEng)--Stellenbosch University, 2015. / ENGLISH ABSTRACT: The operation and optimisation of a distillation train directly effects the total energy consumption of a typical processing plant. With this in mind, the efficient separation of low molecular weight alcohol azeotropes, using heterogeneous azeotropic distillation, is of great economic and environmental importance.
Heterogeneous azeotropic distillation involves the addition of an extraneous component, known as an entrainer, to the mixture to facilitate separation. Benzene has long been replaced as the entrainer of choice, due to its carcinogenic nature, and research into finding a more suitable entrainer has commenced. To determine if an entrainer is suitable for a particular separation, detailed phase behaviour information of the ternary alcohol/entrainer/water system is required; vapour-liquid (VLE), vapour-liquid-liquid (VLLE) equilibria data and the composition of all azeotropes present. This is complicated by the fact that thermodynamic models (like the nonrandom two-liquid (NRTL), universal functional (UNIFAC) and universal quasichemical (UNIQUAC) activity coefficient models) often fail to predict the phase equilibria of ternary systems. The lack of available experimental phase equilibria data, and the inability of thermodynamic models to predict phase equilibria data, has fueled the need for the experimental determination of accurate, repeatable isobaric VLE, VLLE and azeotropic data. With this in mind, this research is focused on the experimental determination of VLE, VLLE and azeotropic data for three low molecular weight alcohol/entrainer/water systems at 101.3 kPa.
Following an extensive literature study on azeotropes, applicable separation techniques and available VLE and VLLE data in literature, the ethanol/2-butanone/water, n-propanol/2-butanone/water and iso-propanol/2-butanone/water systems were chosen for experimental investigation. The experimental determination was carried out in a Gillespie type still, equipped with an ultrasonic homogenizer. The temperature and pressure accuracies of the equipment were found to be 0.03°C and 2mbar respectively. The chosen experimental methodology was verified, and its repeatability tested, through the measurement of isobaric VLE and VLLE data of ethanol/isooctane, ethanol/n-butanol/water and n-propanol/isooctane/water systems at 101.3 kPa and subsequent comparison of the measured data with literature data. The compositional error reported, taking into account experimental and analysis effects, is ±0.014 mole fraction. All experimentally determined data sets, verification and new data, were tested for thermodynamic consistency by using the Wisniak modification of the Herrington test, the L/W consistency test, as well as the McDermott-Ellis consistency test, and found to be consistent. The Othmer-Tobias correlation was used to ensure the measured LLE data followed a steady trend, with all R-values larger than 0.910.
For all three of the new systems chosen, the absence of ternary heterogeneous azeotropes was noted. The presence of a ternary homogeneous azeotrope was found for both the ethanol/2-butanone/water and iso-propanol/2-butanone/water systems. No ternary azeotropes are present for the n-propanol/2-butanone/water system.
Suitable entrainers were compared to 2-butanone (MEK) by plotting measured data and literature information of five similar alcohol/entrainer/water systems on a ternary phase diagram. It was found that MEK could not be considered as a suitable entrainer for heterogeneous azeotropic distillation of ethanol, n-propanol and IPA. This is due to the absence of a ternary heterogeneous azeotrope for the aforementioned alcohol/MEK/water systems.
Finally, the ability of thermodynamic models (NRTL, UNIFAC and UNIQUAC) to predict experimental data was determined both visually and through descriptive statistics. This entailed the inspection of ternary phase diagrams and the calculation and evaluation of average absolute deviation (AAD) and and average absolute relative deviation (AARD%) values. The measured data were modelled in Aspen Plus®. It was found that none of the models could predict the ternary systems with acceptable accuracy and the data were regressed. In general, the regressed parameters for the NRTL, UNIFAC and UNIQAC models improved the model predictions when compared to the built-in Aspen parameters. The UNIFAC model predicted the ethanol/MEK/water and n-propanol/MEK/water systems most accurately while none of the models could predict the IPA/MEK/water systems with acceptable accuracy. / AFRIKAANSE OPSOMMING: Die ontwerp en optimering van 'n distillasietrein het ‘n duidelike effek op die totale energieverbruik van ‘n tipiese prosesaanleg. Met dit in gedagte, is ‘n meer doeltreffende skeiding van lae molekulêre massa alkohol aseotrope, met behulp van heterogene aseotropiese distillasie, voordelig vir die ekonomie en die omgewing.
Heterogene aseotropiese distillasie behels die toevoeging van 'n eksterne komponent, wat bekend staan as 'n skeidingsagent, om uiteindelik die skeiding te fasiliteer deur die komponente se dampdrukke te verander. Benseen was in die verlede ‘n gewilde skeidingsagent, maar dit is a.g.v. sy karsenogeniese eienskappe nie meer aanvaarbaar om te gebruik nie. Nuwe navorsing in hierdie veld fokus dus onder andere op die identifisering van meer geskikte skeidingsagente. Om te bepaal of 'n skeidingsagent geskik is, word indiepte fasegedrag inligting benodig, i.e. damp-vloeistof en damp-vloeistof-vloeistof ewewigsdata en die samestelling van alle aseotrope teenwoordig. Ongelukkig kan termodinamiese modelle dikwels nie die fasegedrag van ternêre stelsels voorspel nie. Dit, sowel as die beperkte beskikbaarheid van eksperimentele ewewigsdata in die literatuur, het dus hierdie navorsing aangevuur. Die projek het gefokus op die experimentele bepaling van damp-vloeistof en damp-vloeistof-vloeistof ewewigsdata en aseotropiese data vir drie alkohol/skeidingsagent/water-stelsels by 101.3 kPa.
Na ‘n indiepte literatuurstudie van aseotrope, gepaste skeidingstegnieke en beskikbare damp-vloeistof en damp-vloeistof-vloeistof ewewigsdata, is 2-butanone (MEK) gekies as ‘n moontlike skeidingsagent en die etanol/MEK/water-, n-propanol/MEK/water- en iso-propanol/MEK/water-stelsels gekies vir eksperimentele ondersoek. Die data is met ‘n dinamiese Gillespie eenheid gemeet, toegerus met ‘n ultrasoniese homogeniseerder om vloeistof-vloeistof skeiding te voorkom. Die akkuraatheidsbande van temperatuur- en druk meetinstrumente was 0,03°C en 2 mbar, onderskeidelik. Die eksperimentele metode en die herhaalbaarheid van metings is bevesting, deur die isobariese damp-vloeistof en damp-vloeistof-vloeistof ewewigsdata van etanol/iso-oktaan, etanol/n-butanol/water en n-propanol/iso-oktaan/water te vergelyk met onafhanklike stelle ooreenstemmende data uit die literatuur. Die gesamentlike eksperimentele en analitiese fout wat gemaak kon word tydens bepaling van molfraksie samestellings was ±0.014 molfraksie. Alle gemete eksperimentele data is getoets vir termodinamiese samehang deur middel van beide die L/W en McDermott-Ellis konsekwentheidstoetse. Die Othmer-Tobias korrelasie is gebruik om seker te maak dat die gemete LLE data ‘n konstante tendens volg, met alle R-waardes groter as 0.910.
Vir al drie van die nuwe stelsels wat gekies is, was ‘n drieledige heterogene aseotroop afwesig. Die teenwoordigheid van drieledige homogene aseotrope is egter waargeneem vir die etanol/MEK/water- en IPA/MEK/water-stelsels. Geen drieledige aseotrope is vir die n-propanol/MEK/water-sisteem gevind nie.
Alle gemete data, asook literatuur inligting van vyf soortgelyke alkohol/skeidingsagent/water sisteme, is op ‘n drieledige fase diagram voorgestel om die skeidingsagente met mekaar te vergelyk. Hiervolgens word dit getoon dat MEK nie as ‘n gepaste skeidingsagent vir heterogene aseotropiese distillase beskou kan word nie a.g.v. die afwesigheid van ‘n drieledige heterogene aseotroop in die voorgenoemde alkohol/MEK/waterstelsels.
Die vermoë van die termodinamiese modelle (NRTL, UNIFAC en UNIQUAC) om die eksperimentele data te voorspel is visueel (per grafiek) sowel as deur beskrywende statistiek bepaal. Dit behels die inspeksie van drieledige fasediagrame en die berekening en evaluasie van die gemiddelde absolute afwyking en gemiddelde absolute relatiewe afwykingswaardes. Hierdie teoretiese data is met Aspen Plus® bepaal. Nie een van die modelle kon die drieledige stelsels se fasegedrag met aanvaarbare akkuraatheid voorspel nie. Die parameters vir die NRTL-,UNIFAC- en UNIQUAC-modelle kan verbeter word deur middel van regressie, in vergelyking met die ingeboude Aspen parameters. Dit is bevind dat die UNIFAC model die etanol/MEK/water- en n-propanol/MEK/water-stelsel die beste kan voorspel. Nie een van die bogenoemde modelle kon egter die fasegedrag van die IPA/MEK/water-stelsel voorspel nie.
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Characterization and azeotropic distillation of crude wood oilCranford, Richard John, 1960- January 1989 (has links)
The batch distillation of crude wood oil by direct liquefaction was studied; azeotropic distillations and some characterization were also performed. It was found that 26-33 percent of the crude wood oil could be distilled by simple batch vacuum distillations with pressures from 50-300 mm Hg. With the use of ethylene glycol and glycerol 29-85 percent more oil was distilled partly due to the azeotrope formed which allows the oil to boil at a reduced pressure. The water liberated and the polymerization which took place during the distillations were studied. It was found that fluid catalytic cracking bottoms eliminates polymerization when it is co-distilled with the crude wood oil. A novel scheme for the separation of the phenolic fraction by azeotropic distillation is presented.
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Experimental simulation of distillation column profile mapsModise, Tshepo Sehole David 27 March 2008 (has links)
ABSTRACT
One of the most important tasks in the chemical industry is the separation of
multicomponent liquid mixtures into one or more high-purity products. Several
technologies are feasible for this task, either alone or in combination, such as
distillation, extraction, crystallization, ect. Among these, distillation is by far the most
widely spread and has a long history in chemical technology. However, until recently,
there has been no systematic approach for understanding the separation of complex
mixtures where azeotropes and multiple liquid phases may occur.
There has been a growing interest in the use of residue curve and column profiles for
the preliminary design of distillation columns. Residue curves and column profile are
not only used to predict the composition changes in the distillation column but also to
determine the feasibility of the proposed separation. Recently, theory underlying
column profile maps has been developed by Tapp, Holland and co-workers. However
there has been no direct experimental validation of the predictions of the column
profile map theory. The main aim of this thesis is to experimentally verify some of
the predictions of column profile map theory.
A simple experimental batch apparatus has been developed to measure residue curve
maps (RCMs) by Tapp and co-workers, the apparatus was modified so that it could
be used to measure column profile maps (CPMs) in this thesis. CPM theory has
shown that CPMs are linear transforms of the residues curve maps (RCMs). A stable
node which was the apex of a mass balance triangle (MBT) was introduced inside the
MBT, this was done by transforming the RCMs to CPMs using the appropriate
distillate composition xd and reflux ratio R. It was also shown that the saddle point
which was on the boundary of the triangle of the RCM can be shifted inside the MBT
by transforming the RCM to CPM. This is again in accordance with theoretical
predictions of CPM theory.
iv
Residue curves (RCs) and pinch point curves (PPCs) are used to determine the
operation leaves and hence the feasible region for distillation columns operating at a
specific distillate and bottoms composition for all fixed reflux ratio. The operating
leaves were expanded beyond the pinch point curve by varying the reflux ratio from a
higher reflux to a lower reflux ratio. This showed that one can effectively cross the
pinch point curve hence expanding the operating leave.
Finally the importance of experimentally measuring CPMs is demonstrated. Two
thermodynamic models were used to predict the profiles of a complex system. The
binary vapor-liquid equilibrium (VLE) diagrams and the residue curves produced
from using these two thermodynamic models did not predict the same topology. The
composition of the profiles were not the same because there were multiple liquid
phases involved in this system, which made it difficult for the researchers to measure
the correct profiles. Column profile maps were simulated using the different
thermodynamic models, they also showed that there is some discrepancy between the
predictions of the two models.
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Use of 1-ethyl-3-methylimidazolium ethyl sulfate for liquid-liquid equilibria for ternary mixturesMohale, Tshepang January 2017 (has links)
Submitted in fulfilment of the academic requirements of Masters in Applied Sciences (Chemistry), Durban University of Technology, 2017. / This thesis forms part of the Durban University of Technology Thermodynamics Research Unit’s project which is aimed at developing a method for determination of the liquid-liquid equilibria (LLE) data for the azeotrope {methanol + water} with an ionic-liquid (IL) using DSA5000M to assess the efficiency of the ionic liquid to be used in liquid-liquid extractions for the recovery and recycling of methanol from petroleum refinery.
The objective of this study was to determine the liquid-liquid equilibria data of the azeotrope {methanol + water} using 1-ethyl-3-methylimidazolium ethyl sulfate ionic liquid with the intention to recycle methanol from the Fischer-Tropsch (FT) process by- products in petroleum industries and to utilize it in gasoline additives in a new methanol to gasoline (MTG) petroleum process.
LLE studies of systems containing alcohols and water are important due to the increasing demands of oxygenated compounds to produce lead free gasoline.
Light alkanols such as methanol and ethanol are reported to be suitable compounds in order to produce lead free gasoline, but the use of methanol in gasoline blends can cause phase separation problems in:
1. dry conditions, these are due to its partial solubility in saturated hydrocarbons.
2. the presence of water from ambient humidity or in storage tanks, this depend on unfavourable distribution factor between aqueous and the hydrocarbon phase.
To determine the possibility of separating methanol from water using ionic liquid, the liquid-liquid equilibria data was determined at room temperature, T = 298.15 K and atmospheric pressure to investigate whether it separate from water and/or a non-phase separation if it is used as an additive.
The experimental data generated was compared to that of the literature for the system
{methanol (1) +toluene (2) + dodecane (3)} and showed good agreement with the literature data with only maximum deviation of ± 0.0015 in the mole fraction using density calculations and ± 0.0092 in the mole fraction when using refractive index calculations The selectivities and distribution coefficients for this system were also calculated and the maximum deviation between the two methods (nD and ρ) was ± 1.33 in selectivities and found to be ±0.001 for distribution coefficients. The maximum deviation in distribution coefficients from literature when using nD calculations for system 1 was ±0.04 and ±0.01 for ρ. For the selectivity values the deviation from that of literature of nD when compared was found to be ± 1.28 and 0.29 for ρ respectively.
The selectivity values from the density calculations were found to be in the range 2.82 –
7.66 for this system with the distribution coefficient values reported in the range 0.17 – 0.23.
In the second system (system 2) the generated experimental data was also compared to that of the literature for the system {water (1) + methanol (2) + cyclohexane (3)} and in good agreement with literature values with only maximum deviation of ± 0.0091 in the weight fraction based on density calculations. The selectivities and distribution coefficients were also calculated and the maximum deviation between the literature and the experimental data was computed to be at ± 0.0003 for selectivity and ±0.09 in distribution coefficient.
The selectivity values were found to be in a range 0.00 - 0.04 for this system and were constant throughout the phases but significantly less than one; with the distribution coefficient values in the range 0.00 – 0.008.
For 1-ethyl-3-methylimidazolium ethyl sulfate system (Ionic liquid system) the selectivity values were not constant throughout the two-phase region and the values were found to be in the range 0.63 -0.99 still below one which indicates that the ionic liquid used in this study could not be considered as a potential solvent for the separation of the investigated azeotrope.
The distribution coefficients for this system were determined and found to be in the range 0.23 – 0.74.
The certainty and reliability of experimentally measured tie-line data was ascertained by applying Othmer-Tobias (OT) correlations and the Non-Random, Two Liquid (NRTL) parameters.
The OT correlations for system 1 was linear and indicated the certainty of the five tie-lines prepared for this system.
In system 2 the OT correlation was not linear and indicated extensively high errors as well as high systematic multiplicative and additive errors in calculations of mole fractions.
For the IL system the OT correlation was linear throughout the whole tie-line range and indicated the adequate precision, which denotes that the investigation was carried out with minimal random and systematic errors and indicated the efficiency of the DSA 5000 M to generate the liquid-liquid equilibria data.
All the ternary systems were well correlated and in good agreement with the estimated NRTL data.
It was only system 1{methanol (1) + toluene (2) + dodecane (3)} that gave a high maximum deviation ( %RSMD) of 1.288 when using the RI measurements with the minimum error margin of 0.6320, this account as to why RI measurements were not applied in other systems (system 2 and ionic liquid system).
Similarly for the same system; system 1{methanol (1) + toluene (2) + dodecane (3)} when using the density measurements; the NRTL model gave a maximum deviation of 0.5620 and minimum error margin of 0.2590.
The NRTL obtained for system 2 {water (1) + methanol (2) + cyclohexane (3)} gave the maximum deviation of 0.5752 and minimum error margin of 0.0127.
The NRTL for the ionic liquid ternary system {[EMIM][EtSO4](1) + methanol (2) + water (3)}showed a good agreement between the experimental data and the NRTL model tie- line data with the %RSMD of 1.0201 on the upper limit and 0.1620 as a lower deviation. / M
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