Supercritical fluid (SF) technologies are being investigated extensively by the food industry for a variety of applications. Carbon dioxide in the supercritical state is of particular interest to the food industry due to its extremely low toxicity in comparison with organic solvents. Three applications of chromatography or extraction employing SFs in the analysis of food components and natural products were investigated. These applications related to carbohydrate, lipid, and coumarin derivative analyses. The peracetylated nitrogen derivatives of carbohydrates were analyzed by supercritical fluid chromatography (SFC) with flame ionization detection (FID), Fourier-transform infrared (FT-IR) detection, and mass spectrometry (MS) detection. Although reports in the literature indicated that only one derivatized component was detected under GC conditions, the SFC analysis of peracetylated aldonitrile derivatives of monosaccharides resulted in detection of multiple reaction products. The identification of the peracetylated nitrile and acyclic oxime was accomplished using both SFC/FT-IR and SFC/MS. The spectroscopic data indicated that an additional reaction product was a peracetylated cyclic oxime. The data was not conclusive enough to determine if the structure contained a pyranose or furanose ring. Changes in chemical composition of vegetable oils due to processing were observed employing SFC/FT-IR. Refined soybean oil and soybean oil that was hydrogenated with a NI or a Ni-S catalyst were analyzed. SFC/FT-IR provided an opportunity to determine the extent of unsaturation and isomerization in a single analysis. The C-H deformation of trans R₁HC=CHR₂ groups was observed at 972 cm⁻¹. The double bond in the cis configuration was evident by absorptions above 3000 cm⁻¹l. On-line FT-IR spectra of triacylglycerols and free fatty acids readily revealed conversion to trans isomers in those samples that were hydrogenated with the Ni-S. Quantitation was not possible due to the incomplete resolution of the cis and trans isomers present in the hydrogenated samples. Apparent threshold densities were determined for a series of coumarin derivatives using a supercritical fluid chromatograph with a flame ionization detector. The extraction cell was a LC stainless steel precolumn. Milligram quantities of the model compounds were extracted. Functionality, extraction temperature, and matrix affected the measured threshold densities of the compounds. The addition of two hydroxyl groups onto the coumarin structure caused the compound to be unextractable at 60°C and densities up to 0.90 g/mL. For those compounds that were completely extracted, coumarin, 7-methoxycoumarin, 3-phenylcoumarin, and psoralen, the apparent threshold density increased with increasing melting point. The melting or decomposition points of those compounds that were partially extracted ranged between 200 and 240°C. For those compounds that were not extracted, under the constraints of the experiment, the melting or decomposition points were greater than 240°C. A higher extraction temperature resulted in a lower threshold density. Corn starch was found to be a noninteractive matrix. / Ph. D.

Compressed and supercritical fluids, such as pressurized CO2, ethane, orpropane, provide a versatile and environmentally acceptable alternative to conventionalliquid organic solvents in bioprocessing applications – specifically in the areas ofproduct extraction, protein purification, microbial sterilization, and enzymatic and wholecellbiocatalysis. While their advantages have been well demonstrated, the effects ofcompressed and supercritical fluids on whole cells are largely unknown.Metabolic and structural perturbations of whole cells by compressed andsupercritical fluid solvents were examined. These perturbations exist as cell metabolismand membrane structure are influenced by pressure and the presence of a solventphase. Continuous cultures of Clostridium thermocellum (a model ethanol-producingthermophilic bacterium) were conducted under elevated hydrostatic and hyperbaricpressure to elucidate pressure- and solvent-effects on metabolism and growth.Fluorescence anisotropy was employed to study liposome fluidization due to thepresence of compressed and supercritical fluids and their partitioning/accumulation inthe phospholipid bilayer.Under elevated hydrostatic pressure (7.0 and 13.9 MPa; 333 K), significantchanges in product selectivity (towards ethanol) and growth were observed in C.thermocellum in conjunction with reduced maximum theoretical growth yields andincreased maintenance requirements. Similarly, metabolism and growth were greatlyinfluenced under hyperbaric pressure (1.8 and 7.0 MPa N2, ethane, and propane; 333K); however, severe inhibition was observed in the presence of supercritical ethane andliquid propane. These changes were attributed to mass-action effects on metabolicpathways, alterations in membrane fluidity, and the dominant role of phase toxicityassociated with compressed and supercritical fluids.Fluorescence anisotropy revealed fluidization and melting point depression ofdipalmitoylphosphatidylcholine liposomes in the presence of CO2, ethane, and propane(1.8 to 20.7 MPa; 295 to 333 K). The accumulation of these fluids within the bilayerupon pressurization and the ordering effects of pressure influenced liposome fluidity, themelting temperature, and the gel-fluid phase transition region. These resultsdemonstrate the disordering effects of compressed and supercritical fluids on biologicalmembranes and the ability to manipulate liposomes.

Supercritical fluid chromatography has recently been coupled to an ICPMS detector. The method has been shown to be suitable for the speciation and analysis of organometallic compounds at trace levels. This study has attempted to further the research initiated by other groups in this field by developing a new interface for coupling these two instruments. The new interface makes use of a modified join between the nebuliser and the torch in the ICP unit. The effect of the mobile phase on the plasma with time has been investigated and little spectral background interference has been observed. The chromatographic conditions were optimised using a flame ionisation detector and a series of tin, arsenic, iron, and mercury compounds were analysed using SFC-ICPMS. Mter focusing the ICP-MS on the element of interest, each compound was evaluated in terms of the change in peak intensity with change in concentration and the theoretical detection limits were compared to the practical detection limit. The restrictor temperature was determined using a rough calibration procedure with bench top experiments. The effect of the restrictor temperature on the peak intensity of each compound was then studied. All results were plotted and a theory for the observed trends and observations is proposed. The results obtained and the interface used have been compared to the results and interfaces of other groups and differences have been explained. Attempts to extract relevant compounds from topsoil using supercritical fluid extraction were made. Finally, sediment samples were collected from relevant points in Durban Bay and an attempt was made to extract these samples using supercritical fluid extraction. The extracted samples were analysed using SFC-ICPMS although little success was obtained. Reasons for the failure of this method on the real samples have been proposed. In the concluding section of this study SFC~ICPMS has been evaluated in terms of its future applicability and use as a viable analytical method. / Thesis (M.Sc.-)-University of Natal, Durban, 1994.

O esgotamento das reservas de petróleo, bem como o impacto ambiental que o seu processamento provoca, tem induzido a busca por fontes alternativas de energia para substituir os fósseis de petróleo como combustível automotivo. No Brasil, o crescimento do agronegócio e o consequente uso dos seus produtos e resíduos de fontes vegetais, favoreceram incríveis descobertas tais como matérias-primas para biocombustíveis, incluindo bioetanol derivado de cana de açúcar e biodiesel de óleos vegetais. Neste sentido, o biodiesel tem recebido bastante destaque nos últimos anos. O objetivo do presente estudo foi a para produção de biodiesel de óleo de soja empregando metanol ou etanol como álcoois pressurizados, além da análise da influencia da adição de água nas melhores condições alcançadas. Para tal, uma unidade experimental de bancada foi construída. Para investigação das variáveis que influenciam o rendimento das reações no sistema estudado, um planejamento fatorial 23 foi adotado, no qual foram investigados os efeitos da temperatura (180 e 300°C), do tempo de residência (10 minutos e 1 hora), da razão molar óleo:etanol (1:10 e 1:50), e da concentração de água (0 a 10% massa em relação ao óleo) sobre a conversão em ésteres da reação, que foi monitorada por cromatografia gasosa de alta resolução. Observou-se que a temperatura tem forte influência na conversão em ésteres da reação, com os melhores resultados para metanol ou etanol (95% de conversão) tendo sido obtidos na temperatura de 300°C. A adição de agua (2,5 e 5,0% em relação ao óleo) ocasionou um leve aumento na conversão (98%) para ambos metanol e etanol. Então, conclui-se então, que condições similares no rendimento do biodiesel de óleo de soja em reator batelada foi obtido utilizando metanol ou etanol pressurizados em condições supercriticas. Este trabalho também propõe uma nova metodologia para análise de acilgliceróis. / The depletion of petroleum reserves coupled with the environmental impact caused by the form of its industrial processing lead a frantic search for alternative energy sources to replace fossil petroleum as automotive fuel. In Brazil, the growth of agribusiness and the consequent use of its products and resides of vegetable sources, brought exciting discoveries such as feedstock biofuels, including bioethanol derived from sugar cane and biodiesel from vegetable oil. In this since, the biodiesel has been receiving singular attention at last years. The objective of this present study was producing biodiesel from soybean oil using methanol or ethanol as alcohol pressurized beyond the analysis of the influence of added water under optimum conditions achieved. For such, an experimental unity was built. To investigate the variables influencing in the yield of the reaction in the system studied, an experimental planning using 23 arranged was adopted, in which was investigated the effects of temperature (220 and 300°C) residence time (10 minutes and 1 hour) and molar ration (oil/alcohol) (1:10 and 1:50). After, the addition of water to the system (0 to 10% in relation to oil) was also evaluated on the conversion to esters, which was monitored by high resolution gas chromatography. It was observed that temperature has a strong influence on the conversion of esters with the best results for methanol or ethanol (95% conversion) were obtained at a temperature of 300°C. Addition of water (2,5 and 5,0% in relation to oil) caused a slight increase in conversion (98%) for both methanol and ethanol. Then was concluded that similar results in the yields of biodiesel from soybean oil in batch reactor was obtained from both methanol or ethanol pressurized as supercritical conditions. This work proposes a new methodology for acylglycerols analysis.

The recovery of organometallic catalysts from polymer matrices is of great importance in promoting the application of homogeneous catalysts in industry. Such a green recovery technique will not only popularize the techniques of green catalytic hydrogenation of polymers by Rempel’s group, but also consummates the technique of heterogenization of organometallic catalysts. The high value product of hydrogenated nitrile butadiene rubber (HNBR) with dissolution of Wilkinson’s catalyst [RhCl(TPP)3] was selected as the model polymer matrix for developing a green separation technique. The supercritical carbon dioxide (scCO2) soluble fluorous Wilkinson’s catalyst [RhCl(P(p-CF3C6H4)3)3] was synthesized and shown exhibit a very limited activity in the catalytic hydrogenation of bulk HNBR. Its recovery from a HNBR matrix using scCO2 however failed. In spite of the assistance of the scCO2 dissolvable chelating ligand thenoyltrifluoroacetone (TTA), the weak compatibility of scCO2 with rhodium complexes failed again as an extraction solvent for the HNBR matrix. Inspired by the merits of CO2-expanded liquids (CXLs) and the versatility of CO2 in changing the physical properties of polymer melts, CXLs were tested as extracting solvents for separation of Wilkinson’s catalyst from bulk HNBR. CO2-expanded water (CXW) and CO2-expanded alcohols including methanol and ethanol (CXM and CXE) were examined with the assistance of a variety of chelating agents. The investigated chelating agents include ethylenediaminetetraacetic acid (EDTA), ethylenediaminetetraacetic acid disodium salt (EDTA-Na2), diethylenetriamine (DETA), N,N,N',N',N"-pentamethyldiethylenetriamine (PMDETA), and N,N,N’,N’-tetramethylethylenediamine (TMEDA). CXM and PMDETA were recognized as the optimal combination of extracting solvent and chelating agent for recovery of Wilkinson’s catalyst from HNBR. An extraction system consisting of CXM and PMDETA was carefully investigated with respect to the effects of temperature and pressure on the extraction performance over the temperature range of 40 to 100 °C and the pressure range of 20 to 200 bar. Increasing temperature effectively increased the extraction rate and became less influential when the temperature was above 80 °C. Increasing pressure at a fixed temperature was found to improve the extraction rate followed by suppressing it. Nevertheless, further increasing the pressure to an extreme high value above the respective critical point was able to promote the extraction rate again. The complex effects of pressure were thoroughly investigated by the means of analyzing the dissolution behavior of CO2 in HNBR and the variation of the extraction phase composition at different operational conditions. 0.14 g/mL was determined as the CO2 density by which the optimal pressure at a fixed temperature can be estimated. Based on a careful interpretation of the experimental results, an extraction mechanism was illustrated for interpreting the present extraction system. Additionally, the reactions involved in the extraction process were illustrated to reveal the principal challenges present in the extraction process and pointed out the potential solution for eliminating the obstacles. Two special operations-sequential operation and pressure varying procedure were tested for their effectiveness in enhancing the extraction ratio. A pressure varying procedure was found to be beneficial in further improving the extraction ratio, while sequential operation did not show any promise in enhancing the recovery. At last, the developed technique was shown to be highly efficient in applying it to HNBR particles coagulated from the HNBR latex. A residue of 59 ppm rhodium was obtained after 9 hours of operation. This study establishes a technology platform for separating the expensive catalyst from the polymer matrix, using “green” CO2-expanded liquids.

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The recovery of organometallic catalysts from polymer matrices is of great importance in promoting the application of homogeneous catalysts in industry. Such a green recovery technique will not only popularize the techniques of green catalytic hydrogenation of polymers by Rempel’s group, but also consummates the technique of heterogenization of organometallic catalysts. The high value product of hydrogenated nitrile butadiene rubber (HNBR) with dissolution of Wilkinson’s catalyst [RhCl(TPP)3] was selected as the model polymer matrix for developing a green separation technique. The supercritical carbon dioxide (scCO2) soluble fluorous Wilkinson’s catalyst [RhCl(P(p-CF3C6H4)3)3] was synthesized and shown exhibit a very limited activity in the catalytic hydrogenation of bulk HNBR. Its recovery from a HNBR matrix using scCO2 however failed. In spite of the assistance of the scCO2 dissolvable chelating ligand thenoyltrifluoroacetone (TTA), the weak compatibility of scCO2 with rhodium complexes failed again as an extraction solvent for the HNBR matrix. Inspired by the merits of CO2-expanded liquids (CXLs) and the versatility of CO2 in changing the physical properties of polymer melts, CXLs were tested as extracting solvents for separation of Wilkinson’s catalyst from bulk HNBR. CO2-expanded water (CXW) and CO2-expanded alcohols including methanol and ethanol (CXM and CXE) were examined with the assistance of a variety of chelating agents. The investigated chelating agents include ethylenediaminetetraacetic acid (EDTA), ethylenediaminetetraacetic acid disodium salt (EDTA-Na2), diethylenetriamine (DETA), N,N,N',N',N"-pentamethyldiethylenetriamine (PMDETA), and N,N,N’,N’-tetramethylethylenediamine (TMEDA). CXM and PMDETA were recognized as the optimal combination of extracting solvent and chelating agent for recovery of Wilkinson’s catalyst from HNBR. An extraction system consisting of CXM and PMDETA was carefully investigated with respect to the effects of temperature and pressure on the extraction performance over the temperature range of 40 to 100 °C and the pressure range of 20 to 200 bar. Increasing temperature effectively increased the extraction rate and became less influential when the temperature was above 80 °C. Increasing pressure at a fixed temperature was found to improve the extraction rate followed by suppressing it. Nevertheless, further increasing the pressure to an extreme high value above the respective critical point was able to promote the extraction rate again. The complex effects of pressure were thoroughly investigated by the means of analyzing the dissolution behavior of CO2 in HNBR and the variation of the extraction phase composition at different operational conditions. 0.14 g/mL was determined as the CO2 density by which the optimal pressure at a fixed temperature can be estimated. Based on a careful interpretation of the experimental results, an extraction mechanism was illustrated for interpreting the present extraction system. Additionally, the reactions involved in the extraction process were illustrated to reveal the principal challenges present in the extraction process and pointed out the potential solution for eliminating the obstacles. Two special operations-sequential operation and pressure varying procedure were tested for their effectiveness in enhancing the extraction ratio. A pressure varying procedure was found to be beneficial in further improving the extraction ratio, while sequential operation did not show any promise in enhancing the recovery. At last, the developed technique was shown to be highly efficient in applying it to HNBR particles coagulated from the HNBR latex. A residue of 59 ppm rhodium was obtained after 9 hours of operation. This study establishes a technology platform for separating the expensive catalyst from the polymer matrix, using “green” CO2-expanded liquids.

Research was conducted into using supercritical fluid extraction (SFE) for removing hydrocarbons from drill cuttings slurries, which will be used in a pilot-scale continuous SFE system currently under development. A laboratory-scale batch SFE system employing supercritical carbon dioxide (CO2) was used in this research. Based on the measured hydrocarbon solubility and apparent hydrocarbon solubility in supercritical CO2, conditions of 14.5 MPa and 40oC were selected for SFE treatment. The slurries require a minimum water to drill cuttings ratio of 1:1 (mass basis) to be free-flowing and therefore suitable for treatment in a continuous system. Water in the slurries leads to lower hydrocarbon extraction efficiencies during SFE treatment compared to the treatment of drill cuttings without slurrying. However, effective mixing and introduction of the supercritical CO2 at the bottom of the extraction vessel resulted in treated slurries containing less than 1% hydrocarbons (dry mass basis). / Environmental Engineering