Rudolf Eggers

Mass transfer in polymers in a supercritical CO2-atmosphere

Abstract Diffusion in poly-(ethylene-terephthalate) (PET), during treatment in a supercritical CO2-atmosphere, was investigated in order to achieve a better understanding of the mass transfer mechanism in the amorphous regions of polymers. Recently, some promising applications have been developed where mass transfer in the polymer phase by means of a supercritical fluid is of major importance. Examples are the dyeing of PET with supercritical CO2, membrane separations of gas–fluid mixtures and the treatment of polymers with supercritical fluids to change their properties (generation of foams, extraction of impurities, etc.). A new experimental method to determine diffusion coefficients has been developed. It is based on the gravimetric measurements of mass transport with a simultaneous investigation of the swelling behavior of PET in supercritical CO2, on a single polymer sample. The swelling of PET was compared with the swelling behavior of another glassy polymer (bisphenol-A polycarbonate) in supercritical CO2. Experimental data of the sorption of CO2 and different kinds of disperse dyes in the polymeric matrix have been measured in order to calculate diffusion coefficients for the different substances. The diffusion coefficients have been calculated by a classical diffusion model for cylindrical solids. It could be shown that diffusion of disperse dyes in PET strongly depends on the dye itself, which is key information for the process development.

High pressure extraction of oil seed

For calculation of phase equilibria of the system seed oil/CO2, an equation of state published in the literature has been fitted to experimental data of that system. The results thus obtained are of only limited use in designing a supercritical extraction process. The experimental investigation of the mass transfer kinetics is much more significant. Mechanical processing of the oil seed’s cell wall structure has been shown to be of great importance. The best specific yields were achieved with material that had been mechanically pre-deoiled and thereby broken open. Yields are increased considerably by use of the gas mixture CO2/propane or other special gas mixtures or by the addition of refrigerants. However, the extraction times achieved in batch operation, together with the mass product nature of oil seed, make a continuous supercritical extraction essential if operation is to become economic relative to the conventional hexane extraction. To this end, the energetics of the process have been calculated, and practical possibilities for continuous operation are discussed.

Quantitative Investigation of Trigonelline, Nicotinic Acid, and Nicotinamide in Foods, Urine, and Plasma by Means of LC-MS/MS and Stable Isotope Dilution Analysis

A straightforward stable isotope dilution analysis (SIDA) for the quantitative determination of trigonelline, nicotinic acid, and nicotinamide in foods such as coffee, as well as in biological samples by means of LC-MS/MS (MRM) has been developed. The coefficients of variation for their quantitative analysis in a coffee sample were 2.1% for trigonelline, 1.1% for nicotinic acid, and 3.1% for nicotinamide, and recovery experiments showed good results between 98.5 and 104.5%. Application of this SIDA for the quantification of trigonelline, nicotinic acid, and nicotinamide in coffee samples of different roasting degrees revealed a drastic degradation of trigonelline as well as the generation of nicotinic acid accounting for 4-6% of the initial trigonelline content, whereas nicotinamide remained rather constant at a low level. Besides the analysis of coffee samples, the feasibility of the developed SIDA was verified by analysis of other foods including breakfast cereals, rice, liver, and herring, as well as human urine and plasma samples.

Density and volume of water and triglyceride mixtures in contact with carbon dioxide

The density and volume of vegetable oils and water in contact with carbon dioxide and nitrogen have been measured with a magnetic suspension balance coupled with a high pressure view cell. Pressure and temperature were varied from atmospheric pressure to about 30 MPa and from room temperature to 80°C, respectively. The density of water, corn oil and palm oil increases with increasing pressure by up to about 5%. The volume increases up to about 6% for water and up to about 45% for corn oil and palm oil, due to the solvation of carbon dioxide.

Development of a Hydrophilic Liquid Interaction Chromatography−High-Performance Liquid Chromatography−Tandem Mass Spectrometry Based Stable Isotope Dilution Analysis and Pharmacokinetic Studies on Bioactive Pyridines in Human Plasma and Urine after Coffee Consumption

The paper reports on the development of an accurate hydrophilic liquid interaction chromatography tandem mass spectrometry (HILIC-MS/MS) based stable isotope dilution analysis for the simultaneous quantitation of the food-derived bioactive pyridines trigonelline, nicotinic acid, nicotinamide, and N-methylpyridinium, as well as their key metabolites nicotinamide-N-oxide, N-methylnicotinamide, N-methyl-2-pyridone-5-carboxamide, N-methyl-4-pyridone-5-carboxamide, and N-methyl-2-pyridone-5-carboxylic acid in human plasma and urine. Precision of the stable isotope dilution analysis (SIDA) was 1.9% and 11.9% relative standard deviation (n = 6), and accuracy was between 92.4% and 113.0%. The lower limit of quantitation (LLOQ) was 50 fmol (10 pmol/mL) injected onto the column for all analytes with the exception of N-methyl-2-pyridone-5-carboxylic acid and N-methyl-2-pyridone-5-carboxamide, for which an LLOQ of 100 fmol (20 pmol/mL) was found. The method was applied to monitor the plasma appearance and urinary excretion and to determine pharmacokinetic parameters of the bioactive pyridines as well as their metabolites in a clinical human intervention study with healthy volunteers (six women, seven men) after oral administration of 350 mL of a standard coffee beverage. Trigonelline plasma levels increased from 160 nmol/L to maximum concentrations of 5479 (males) or 6547 nmol/L (females), and N-methylpyridinium plasma levels raised from virtually complete absence to maximum values of 777 (females) or 804 nmol/L (males) within 2-3 and 1-2 h after coffee consumption, respectively. The high plasma levels of N-methylpyridinium found after coffee consumption clearly demonstrate for the first time that this cation is entering the vascular system, which is the prerequisite for biological in vivo effects claimed for that compound. In contrast, the coffee intervention did not significantly influence the plasma concentrations of N-methyl-2-pyridone-5-carboxamide and N-methyl-4-pyridone-5-carboxamide, the major niacin metabolites. Within 8 h after coffee intervention, an urinary excretion of 57.4 +/- 6.9% of trigonelline and 69.1 +/- 6.2% of N-methylpyridinium was found for the male volunteers, whereas females excreted slightly less with 46.2 +/- 7.4% and 61.9 +/- 12.2% of these pyridines.

Extraction/fractionation and deacidification of wheat germ oil using supercritical carbon dioxide

Wheat germ oil was obtained by mechanical pressing using a small-scale screw press and by supercritical extraction in a pilot plant. With this last method, different pressures and temperatures were tested and the tocopherol concentration in the extract was monitored during extraction. Then supercritical extracted oil as well as commercial pressed oil were deacidified in a countercurrent column using supercritical carbon dioxide as solvent under different operating conditions. Samples of extract, refined oil and feed oil were analyzed for free fatty acids (FFA) and tocopherol contents. The results show that oil with a higher tocopherol content can be obtained by supercritical extraction-fractionation and that FFA can be effectively removed by countercurrent rectification while the tocopherol content is only slightly reduced.

Disintegration of liquid jets and drop drag coefficients in pressurized nitrogen and carbon dioxide

The aim of this investigation is to clarify of the basic phenomena at the disintegration of liquid jets in a pressurized gas at up to 35 MPa. This is carried out by the characterization of the forces involved in the disintegration of liquid jets, which are influenced by the physical properties of the phases used.

Interfacial tensions of ethanol–carbon dioxide and ethanol–nitrogen. Dependence of the interfacial tension on the fluid density—prerequisites and physical reasoning

Abstract Interfacial tensions in the systems ethanol–carbon dioxide and ethanol–nitrogen are measured. In both systems the interfacial tension decreases with increasing pressure. The interfacial tension in the system ethanol–nitrogen decreases with increasing temperature. In contrast to this, in the system ethanol–carbon dioxide at high pressures an isobaric increase in temperature provokes an increase in interfacial tension. In the system ethanol–carbon dioxide at elevated pressure the density of the carbon dioxide phase is the only influence parameter concerning the interfacial tension. This phenomena can be observed for various other systems with one near critical or supercritical component and a high solubility of this component in the liquid phase and at temperatures above the critical temperature of the gas. For this fact a physical reasoning, which is based on a new concept of partial interfacial tensions, is given. Furthermore, it is stated that the interfacial tension of fatty systems in contact with carbon dioxide has approximately the same dependence on the reduced density (ρr=ρ/ρc) of the supercritical phase as the interfacial tension of the same systems in contact with ethane. The knowledge of this fact can help to avoid experiments with ethane, which is flammable.

Adsorption kinetics of surfactant mixtures from micellar solutions as studied by maximum bubble pressure technique.

The adsorption kinetics of micellar solutions of anionic/cationic SDS/DATB mixtures with mixing ratios of 10/1 and 10/2, respectively, are studied experimentally by means of the maximum bubble pressure method. For long adsorption times the adsorption of the highly surface-active anionic/cationic complex leads to a decrease of dynamic surface tension in comparison to the single SDS system. However, the situation is the reverse for short adsorption times where the dynamic surface tension is increased by addition of the cationic surfactant, although the overall concentration is increased. This unexpected behavior is explained by partial solubilization of free SDS molecules into micelles formed by SDS/DTAB complexes. With increasing overall concentration, when eventually the CMC of SDS is reached, the anionic/cationic complex itself is solubilized by SDS micelles. Finally, no complex micelles, which for their part can solubilize an excess of SDS molecules, are present. Hence, the dynamic properties of the solution are no longer influenced by the depletion of SDS molecules and the mixture tends to behave like a pure SDS solution.

Special features of SCF solid extraction of natural products: deoiling of wheat gluten and extraction of rose hip oil

Supercritical CO2 extraction has shown great potential in separating vegetable oils as well as removing undesirable oil residuals from natural products. The influence of process parameters, such as pressure, temperature, mass flow and particle size, on the mass transfer kinetics of different natural products has been studied by many authors. However, few publications have focused on specific features of the raw material (moisture, mechanical pretreatment, bed compressibility, etc.), which could play an important role, particularly in the scale-up of extraction processes. A review of the influence of both process parameters and specific features of the material on oilseed extraction is given in Eggers (1996). Mechanical pretreatment has been commonly used in order to facilitate mass transfer from the material into the supercritical fluid. However, small particle sizes, especially when combined with high moisture contents, may lead to inefficient extraction results. This paper focuses on the problems that appear during scale-up in processes on a lab to pilot or industrial plant scale related to the pretreatment of material, the control of initial water content and vessel shape. Two applications were studied: deoiling of wheat gluten with supercritical carbon dioxide to produce a totally oil-free (< 0.1 % oil) powder (wheat gluten) and the extraction of oil from rose hip seeds. Different ways of pretreating the feed material were successfully tested in order to develop an industrial-scale gluten deoiling process. The influence of shape and size of the fixed bed on the extraction results was also studied. In the case of rose hip seeds, the present work discusses the influence of pretreatment of the seeds prior to the extraction process on extraction kinetics.