Supercritical fluid extraction of paraffin wax

Crause, J. C. (James Christoffel) (2001-12)

Thesis (PhD)--University of Stellenbosch, 2001.

Thesis

ENGLISH ABSTRACT: In this study the deoiling and fractionation of paraffin wax using supercritical fluid extraction (SCFE) has been investigated. SCFE was compared with state-of-the-art processes such as wax crystallisation, static crystallisation and short path distillation. Ethane and carbon dioxide were investigated as supercritical solvents for the supercritical fluid extraction of paraffin wax. Supercritical phase equilibrium data for ethane - n-alkane and CO2 - n-alkane systems close to the mixture critical region were obtained from the literature, and were correlated with several equations of state. Statistical mechanical equations of state failed to correlate the data close to the mixture critical region due to the neglect of density fluctuations which influences phase behaviour close to critical points, or due to inadequate mixing rules. It was found that simple cubic equations of state such as Soave-Redlich-Kwong, Peng-Robinson and Patel-Teja could correlate the data using two interaction parameters. This can be attributed more to their flexibility as correlating tools than to their fundamental accuracy. The Patel-Teja EOS was modified by fitting it to predict low vapour pressure data for long-chain n-alkanes. This modified Patel-Teja EOS was then fitted to the phase equilibria by adjusting two interaction parameters per binary system. The interaction parameters for each solvent (ethane or CO2) system were then fitted to generalised correlations to enable extrapolation to solvent - n-alkane systems for which no equilibrium data were available. The Simplified Perturbed Hardchain theory (SPHC) equation of state was used to correlate lower-pressure solubility data used to model the extract separator. A pilot plant SCFE unit was constructed and used to obtain experimental fractionation data of a low-molecular weight Fischer-Tropsch wax. The experimental results indicate that fractionation of the wax is possible and that the separation efficiency is enhanced by returning some of the extract to the column as reflux. An equilibrium stage model was constructed and used to simulate the extraction experiments. It was possible to obtain good agreement between the experimental results and model predictions. Deoiling of petroleum waxes with a low n-paraffin content (which are not currently deoiled commercially) was investigated. Experimental SCFE and SPD results indicated that selective deoiling is not possible, since the separation is based on differences in molecular weight (or vapour pressure). Simulations of wax crystallisation or solvent extraction and practical tests indicate that deoiling is possible, based on differences in structure and therefore melting point of the components in the wax. Practical problems associated with crystallisation or solvent extraction such as filtration, the use of chlorinated solvents and low yields currently prevent the commercial deoiling of these waxes. During crystallisation of these waxes a soft wax cake is formed which impedes the operation of static crystallisation. A detailed study of the economics of n-paraffin wax deoiling using SCFE was conducted. Flow sheets were proposed to minimise the energy consumption of the SCFE process. Comparison of SPD, static crystallisation and SCFE indicates that a SPD plant will be the cheapest option for deoiling the wax feed investigated. Fractionation of heavier waxes using SPD might not be economically feasible, since the distillation temperature increases dramatically with increasing molecular weight, which leads to higher energy cost. For medium to long chain n-paraffin waxes SCFE should be very competitive, since the capacity of the supercritical solvent can be manipulated to extract longer chain waxes without increasing the extraction temperature. Static crystallisation appears to be the more expensive deoiling option, due primarily to the large initial capital investment cost.

AFRIKAANSE OPSOMMING: Die olieverwydering en fraksionering van paraffienwasse met behulp van superkritiese ekstraksie is in hierdie studie ondersoek. Die modellering van moderne olieverwyderings- en fraksioneringsmetodes soos waskristallisasie, statiese kristallisasie en kortpad distillasie is ook ondersoek. Etaan en koolstofdioksied is ondersoek as superkritiese oplosmiddels vir die superkritiese ekstraksie van paraffienwasse. Literatuurdata van superkritiese fase-ewewigte vir etaan - n-alkaan en CO2 - n-alkaan stelsels naby die mengselkritiese punt is versamel en gekorreleer met verskeie toestandsvergelykings. Statisities-meganiese toestandsvergelykings kon nie data naby mengselkritiese punte korreleer nie, moontlik weens digtheidsvariasies wat afwykings van klassieke gedrag teweegbring, of onakkurate mengreëls. Eenvoudige kubiese toestandsvergelykings soos Soave-Redlich-Kwong, Peng-Robinson en Patel-Teja kon op die ewewigsdata gepas word deur gebruik van twee interaksieparameters. Dit kan eerder toegeskryf word aan hulle buigsaamheid eerder as hulle fundamentele akkuraatheid. Die Patel-Teja toestandsvergelyking is gemodifiseer deur dit te pas op lae dampdruk data van langketting n-alkane. Hierdie gemodifiseerde toestandsvergelyking is gepas op die fase-ewewig data deur twee interaksieparameters te gebruik per binêre sisteem. Die interaksieparameters vir die oplosmiddel stelsels (etaan of CO2) is gekorreleer met algemene vergelykings sodat dit vir ekstrapolasie na oplosmiddel - n-alkaan stelsels gebruik kan word waarvoor ewewigsdata nie beskikbaar is nie. Die "Simplified Perturbed Hardchain" teorie (SPHC) toestandsvergelyking is gebruik om laer druk oplosbaarheidsdata te korreleer vir gebruik in die modellering van die ekstrak skeier. In Superkritiese ekstraksie loodsaanleg is gebou en gebruik om eksperimentele fraksioneringsdata van 'n lae molekulêre massa Fischer- Tropsch was te genereer. Vanaf die eksperimentele resultate blyk fraksionering van was moontlik te wees. Die doeltreffendheid van die skeiding kan verhoog word deur terugvloei van ekstrak na die kolom. 'n Ewewigsmodel is opgestel en gebruik om die ekstraksie eksperimente te modelleer. Deur die ekstraksiedruk en aantal stadia te verander kon goeie ooreenstemming met eksperimentele resultate verkry word. Die verwydering van olie uit petroleumwasse met In lae n-paraffien inhoud (wat nie tans kommersiëel ontolie word nie) is ondersoek. Eksperimentele resultate vir superkritiese ekstraksie en kortpad distillasie dui daarop dat selektiewe olieverwydering nie moontlik is nie, omdat die skeiding gebaseer is op verskille in molekulêre massas en dus (of dampdrukke). Simulasies van waskristallisasie dui op die moontlikheid van olieverwydering gebaseer op verskille in strukture van die komponente in die was. Praktiese probleme geassosieer met kristallisasie of oplosmiddel ekstraksie soos filtrasie, lae opbrengste en gebruik van gechlorineerde koolwaterstowwe as oplosmiddel belemmer die kommersialisering van olieverwydering vir hierdie tipes wasse. 'n Gedetaileerde studie van die ekonomiese lewensvatbaarheid van superkritiese olieverwydering is uitgevoer. Vloeidiagramme is voorgestelom die energieverbruik van die superkritiese ekstraksieproses te minimeer. Vergelyking van kortpad distillasie, statiese kristallisasie en superkritiese ekstraksie dui daarop dat kortpad distillasie die goedkoper opsie vir die olieverwydering van die spesifieke was is. Fraksionering van swaarder wasse met kortpad distillasie sal moontlik nie haalbaar wees nie omdat die distillasietemperatuur drasties toeneem met molekulêre massa. Die skeiding van medium tot langketting wasse met superkritiese ekstraksie behoort meer mededingend te wees, want die kapasiteit van die superkritiese oplosmiddel kan maklik verstel word om langer kettinglengtes wasse te ekstraeer sonder om die temperatuur te verhoog. Statiese kristallisasie blyk die duurder olieverwyderingsopsie te wees hoofsaaklik weens die hoë kapitaalkoste van so 'n aanleg.

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