Preparative separation and purification of sesquiterpenoids from tussilago farfara l. by high-speed counter-current chromatography

Preparative high-speed counter-current chromatography (HSCCC) was successfully applied for separation and purification of sesquiterpenoids from an extract of Tussilago farfara L. with a two-phase solvent system composed of n-hexane-ethyl acetate- methanol-water (1:0.5:1.1:0.3, v/v/v/v). The separation produced a total of 32 mg of tussilagone, 18 mg of 14-acetoxy-7β-(3'-ethyl cis-crotonoyloxy)-lα-(2'-methyl butyryloxy)-notonipetranone and 21 mg of 7β-(3'-ethyl cis-crotonoyloxy)-lα-(2'- methyl butyryloxy)-3,14-dehydro-Z-notonipetranone from 500 mg of the crude extract in one step separation with the purity of 99.5, 99.4 and 99.1%, respectively, as determined by HPLC. The structures of these compounds were identified by ESI-MS, ¹H-NMR and 13C-NMR.

Dispersive liquid-liquid microextraction for the simultaneous separation of trace amounts of zinc and cadmium ions in water samples prior to flame atomic absorption spectrometry determination

In the proposed method, carbon tetrachloride and ethanol were used as extraction and dispersive solvents. Several factors that may be affected on the extraction process, such as extraction solvent, disperser solvent, the volume of extraction and disperser solvent, pH of the aqueous solution and extraction time were optimized. Under the optimal conditions, linearity was maintained between 1.0 ng mL-1 to 1.5 mg mL-1 for zinc and 1.0 ng mL-1 to 0.4 mg mL-1 for cadmium. The proposed method has been applied for determination of trace amount of zinc and cadmium in standard and water samples with satisfactory results.

Separation and characterization of asphaltenic subfractions

The structure of the various asphaltenic subfractions found in crude oil was evaluated. For this purpose, C5 asphaltenes were extracted from an asphaltic residue using n-pentane as the flocculant solvent. The different subfractions were isolated from the C5 asphaltenes by the difference in solubility in different solvents. These were characterized by infrared spectroscopy, nuclear magnetic resonance, X-ray fluorescence, elementary analysis and mass spectrometry. The results confirmed that the subfractions extracted with higher alkanes had greater aromaticity and molar mass. However, small solubility variations between the subfractions were attributed mainly to the variation in the concentrations of cyclical hydrocarbon compounds and metals.

Dispersive liquid-liquid microextraction based on solidification of floating organic drop for simultaneous separation/preconcentration of nickel, cobalt and copper prior to determination by electrothermal atomic absorption spectrometry

A dispersive liquid-liquid microextraction based on solidification of floating organic drop for simultaneous extraction of trace amounts of nickel, cobalt and copper followed by their determination with electrothermal atomic absorption spectrometry was developed. 300 µL of acetone and 1-undecanol was injected into an aqueous sample containing diethyldithiocarbamate complexes of metal ions. For a sample volume of 10 mL, enrichment factors of 277, 270 and 300 and detection limits of 1.2, 1.1 and 1 ng L-1 for nickel, cobalt and copper were obtained, respectively. The method was applied to the extraction and determination of these metals in different water samples.

Preparative separation and purification of bufadienolides from ChanSu by high-speed counter-current chromatography combined with preparative HPLC

Eight bufadienolides were successfully isolated and purified from ChanSu by high-speed counter-current chromatography (HSCCC) combined with preparative HPLC (prep-HPLC). First, a stepwise elution mode of HSCCC with the solvent system composed of petroleum ether - ethyl acetate - methanol - water (4:6:4:6, 4:6:5:5, v/v) was employed and four bufadienolides, two partially purified fractions were obtained from 200 mg of crude extract. The partially purified fractions III and VI were then further separated by prep-HPLC, respectively, and another four bufadienolides were recovered. Their structures were confirmed by ESI-MS and ¹H-NMR spectra.

Separation and preconcentration of copper in environmental samples on Amberlite XAD-8 resin after complexation with a carbothioamide derivative

A new solid phase extraction (SPE) method has been developed for the selective separation and preconcentration of Cu (II) ions in food and water samples prior to its flame atomic absorption spectrometry determination. The method is based on the adsorption of the Cu(II) - 2-{[4-Amino-3-(4-methylphenyl-5-oxo-4,5-dihydro-1H-1,2,4-triazol-1-yl]acetyl}-N-phenyl hydrazinecarbothioamide complex on Amberlite XAD-8 resin. The metal complex retained on the resin was eluted with 7.5 mL of 2.0 mol L-1 HCl in acetone. The optimum conditions for the SPE of Cu(II) ions were investigated, and the method was subsequently applied to sea water, stream water, rice, tea, and tobacco samples for the determination of Cu(II) levels.

Preparative separation of polyphenols from artichoke by polyamide column chromatography and high-speed counter-current chromatography

An efficient method for the rapid separation and purification of polyphenols from artichoke by polyamide column chromatography in combination with high-speed counter-current chromatography (HSCCC) was successfully built. The crude ethanol extracts from dry artichoke were first pre-separated by polyamide column chromatography and divided in two parts as sample 1 and sample 2. Then, the samples were further separated by HSCCC and yielded 7.8 mg of chlorogenic acid (compound I), 24.5 mg of luteolin-7-O-β-D-rutinoside (compound II), 18.4 mg of luteolin-7-O-β-D-glucoside (compound III), and 33.4 mg of cynarin (compound IV) with purity levels of 92.0%, 98.2%, 98.5%, and 98.0%, respectively, as determined by high-performance liquid chromatography (HPLC) method. The chemical structures of these compounds were identified by electrospray ionization-mass spectrometry (ESI-MS) and nuclear magnetic resonance (NMR).

Preparative separation of C19-diterpenoid alkaloids from Aconitum carmichaelii Debx by pH‑zone-refining counter-current chromatography

The technique of pH-zone-refining counter-current chromatography was successfully applied to preparatively separate three C19-diterpenoid alkaloids from the crude extracts of Aconitum carmichaelii for the first time using a two-phase solvent system of petroleum ether-ethyl acetate-methanol-water (5:5:1:9, v/v/v/v). Mesaconitine (I), hypaconitine (II), and deoxyaconitine (III) were obtained from 2.5 g of the crude alkaloids in a one-step separation; the yields were 4.16%, 16.96%, and 5.05%, respectively. The purities of compounds I, II, and III were 93.0%, 95%, and 96%, respectively, as determined by HPLC. The chemical structures of the three compounds were identified by electrospray ionization mass spectrometry (ESI-MS) and NMR.

Separation and purification of three stilbenes from the radix of Polygonum cillinerve (Nakai) Ohwl by macroporous resin column chromatography combined with high-speed counter-current chromatography

An effective method for the rapid separation and purification of three stilbenes from the radix of Polygonum cillinerve (Nakai) Ohwl by macroporous resin column chromatography combined with high-speed counter-current chromatography (HSCCC) was successfully established. In the present study, a two-phase solvent system composed of chloroform-n-butanol-methanol-water (4:1:4:2, v/v/v/v) was used for HSCCC separation. A one-step separation in 4 h from 150 mg of crude extract produced 26.3 mg of trans-resveratrol-3-O-glucoside, 42.0 mg of pieceid-2"-O-gallate, and 17.9 mg of trans-resveratrol with purities of 99.1%, 97.8%, and 99.4%, respectively, as determined by high-performance liquid chromatography (HPLC). The chemical structures of these compounds were identified by nuclear magnetic resonance (NMR) spectroscopy.

Separation of Gas Bubbles from Circulation Waters and Pulp Suspensions in Open Channel Flow

The objective of this thesis was to study the removal of gases from paper mill circulation waters experimentally and to provide data for CFD modeling. Flow and bubble size measurements were carried out in a laboratory scale open gas separation channel. Particle Image Velocimetry (PIV) technique was used to measure the gas and liquid flow fields, while bubble size measurements were conducted using digital imaging technique with back light illumination. Samples of paper machine waters as well as a model solution were used for the experiments. The PIV results show that the gas bubbles near the feed position have the tendency to escape from the circulation channel at a faster rate than those bubbles which are further away from the feed position. This was due to an increased rate of bubble coalescence as a result of the relatively larger bubbles near the feed position. Moreover, a close similarity between the measured slip velocities of the paper mill waters and that of literature values was obtained. It was found that due to dilution of paper mill waters, the observed average bubble size was considerably large as compared to the average bubble sizes in real industrial pulp suspension and circulation waters. Among the studied solutions, the model solution has the highest average drag coefficient value due to its relatively high viscosity. The results were compared to a 2D steady sate CFD simulation model. A standard Euler-Euler k-ε turbulence model was used in the simulations. The channel free surface was modeled as a degassing boundary. From the drag models used in the simulations, the Grace drag model gave velocity fields closest to the experimental values. In general, the results obtained from experiments and CFD simulations are in good qualitative agreement.

Tasasähkönjakeluverkon vaihtosuuntaaja galvaanisella erotuksella

Suomessa sähkönjakeluverkko koostuu pääasiassa 20 kV ja 400 V jännitetasoista. Tällöin sähkö viedään lähelle kuluttajia suuremmalla jännitetasolla ja muunnetaan alhaisemmaksi lähellä asiakkaita. Haittapuolena on se, että haja-asutusalueilla jakelumuuntajien määrä kasvaa suureksi, koska ne täytyy sijoittaa lähelle kuluttajaa. Vaihtoehtona on toteuttaa osa sähkönjakelusta tasajännitteellä, jolloin tehollinen jännite olisi suurempi. Tällöin sähköä voitaisiin siirtää pidempiä matkoja ilman, että asiakaskohtaisia tai muutaman asiakkaan kattavia 20 kV siirtolinjoja tarvitsisi käyttää. Tämä taasen edellyttää asiakaskohtaisien vaihtosuuntaajien käyttöä. Tässä työssä esiteltävällä 1 kVA vaihtosuuntaajalla muodostetaan tasasähköjakeluverkosta saatavasta 750 V tasasähköstä yksivaiheista (230 VRMS, 50 Hz) verkkojännitettä. Laite on suunniteltu toteuttamaan galvaaninen erotus mahdollisimman hyvän hyötysuhteen puitteissa. Vaihtosuuntaaja on toteutettu käyttämällä resonanssikonvertteria, joka vaihtosuuntaa jakelujännitteen korkeataajuiseksi vaihtojännitteeksi. Tämän jälkeen toteutetaan galvaaninen erotus käyttäen suurtaajuusmuuntajaa. Tätä seuraa syklokonvertteri, joka pulssintiheysmodulaatiota soveltaen muodostaa lähtöjännitteen. Tämä suodatetaan lopuksi LC- alipäästösuotimella säröltään standardin mukaiseksi. Laite on jaettu työssä kolmeen osaan, joista jokaisen toiminta on selitetty ja simuloitu itsenäisesti. Lopussa koko järjestelmä on simuloitu yhtenä kokonaisuutena. Hyötysuhteeksi arvioitiin karkeasti 94 % ja lopullisista tuloksista voidaan päätellä, että laitteen toteuttaminen prototyypiksi voisi olla kannattavaa.

Galvaanisen erotuksen toteuttaminen tasavirtasähkönjakelun asiakaspäätelaitteessa

Suomessa sähkönjakeluverkon pääasialliset jännitetasot ovat 20 kV ja 400 V. 20 kV jännitetasolla sähkö viedään lähelle kuluttajia ja muunnetaan pienemmäksi lähellä asiakkaita. Haittapuolena on se, että 20 kV avojohtosähkönsiirtoverkko on hyvin vika-altis ja usein yhden haaran vikaantuessa monta muutakin jää ilman sähköä. Lisäksi hintavien ja suurien jakelumuuntajien määrä on suuri. Vaihtoehtona on toteuttaa osa sähkönjakelusta tasajännitteellä, jolloin tehollinen pienjännite olisi 400 V:a suurempi. Tällöin sähköä voitaisiin siirtää pidempiä matkoja ilman, että asiakaskohtaisia tai muutaman asiakkaan kattavia 20 kV siirtolinjoja tarvitsisi käyttää. Tämä edellyttää vaihtosuuntauksen toteuttamista kuluttajan päässä. Tässä työssä esiteltävällä 1 kVA:n tehoisella vaihtosuuntaajalla muodostetaan tasasähköjakeluverkosta saatavasta 750 V tasasähköstä yksivaiheista (230 VRMS, 50 Hz) verkkojännitettä. Laite on suunniteltu toteuttamaan galvaaninen erotus mahdollisimman hyvällä hyötysuhteella. Suurtaajuusmuuntajan mitoitus mahdollisimman hyvälle hyötysuhteelle on haastava tehtävä, koska vaatimuksia sille asettavat sekä syöttävä resonanssikonvertteri että syötettävä syklokonvertteri. Mitoituksessa on pyrittävä löytämään mahdollisimman hyvä hyötysuhde kustannusten ja toteutettavuuden suhteen.

Modeling of electrolyte sorption – from phase equilibria to dynamic separation systems

In this thesis, general approach is devised to model electrolyte sorption from aqueous solutions on solid materials. Electrolyte sorption is often considered as unwanted phenomenon in ion exchange and its potential as an independent separation method has not been fully explored. The solid sorbents studied here are porous and non-porous organic or inorganic materials with or without specific functional groups attached on the solid matrix. Accordingly, the sorption mechanisms include physical adsorption, chemisorption on the functional groups and partition restricted by electrostatic or steric factors. The model is tested in four Cases Studies dealing with chelating adsorption of transition metal mixtures, physical adsorption of metal and metalloid complexes from chloride solutions, size exclusion of electrolytes in nano-porous materials and electrolyte exclusion of electrolyte/non-electrolyte mixtures. The model parameters are estimated using experimental data from equilibrium and batch kinetic measurements, and they are used to simulate actual single-column fixed-bed separations. Phase equilibrium between the solution and solid phases is described using thermodynamic Gibbs-Donnan model and various adsorption models depending on the properties of the sorbent. The 3-dimensional thermodynamic approach is used for volume sorption in gel-type ion exchangers and in nano-porous adsorbents, and satisfactory correlation is obtained provided that both mixing and exclusion effects are adequately taken into account. 2-Dimensional surface adsorption models are successfully applied to physical adsorption of complex species and to chelating adsorption of transition metal salts. In the latter case, comparison is also made with complex formation models. Results of the mass transport studies show that uptake rates even in a competitive high-affinity system can be described by constant diffusion coefficients, when the adsorbent structure and the phase equilibrium conditions are adequately included in the model. Furthermore, a simplified solution based on the linear driving force approximation and the shrinking-core model is developed for very non-linear adsorption systems. In each Case Study, the actual separation is carried out batch-wise in fixed-beds and the experimental data are simulated/correlated using the parameters derived from equilibrium and kinetic data. Good agreement between the calculated and experimental break-through curves is usually obtained indicating that the proposed approach is useful in systems, which at first sight are very different. For example, the important improvement in copper separation from concentrated zinc sulfate solution at elevated temperatures can be correctly predicted by the model. In some cases, however, re-adjustment of model parameters is needed due to e.g. high solution viscosity.

Sulfuric acid - glucose separation using mixed-recycle steady state recycling chromatography

Batch chromatography is a widely used separation technique in a variety of fields meeting difficult separations. Several technologies for improving the performance of chromatography have been studied, including mixed-recycle steady state recycling (MR-SSR) chromatography. Design of MR-SSR has been commonly limited on 100 % purity constraint cases and empirical work. In this study a predictive design method was used to optimize feed pulse size and design a number of experimental MR-SSR separations for a solution of 20 % sulfuric acid and 100 g/L glucose. The design was under target product fraction purities of 98.7 % for H2SO4 and 95 % for glucose. The experiments indicate a maximum of 59 % increase in sulfuric acid productivity and 82 % increase for glucose when compared to corresponding batch separation. Eluent consumption was lowered by approximately 50 % using recycling chromatography. Within this study the target purities and yields set in design were not completely met, and further optimization of the process is deemed necessary.

Potassium distribution in drip irrigation with fertigation for different injection distances in the main line

The purpose of this research was to evaluate the K2O distribution uniformity by surface drip irrigation at Universitat Politecnica de Valencia, Valencia, Spain (39º 29′ N, 0º 23′ W, 20 m). The irrigation was performed by drip lines with not-compensated emitters, spaced 0.3 m. The fertigation was realized using a fertilizer injector pump of electric action with injection of 0.25 h. The experimental design used completely randomized blocks with five treatments and four replications. The treatments consisted of injection in five distances, located at 10; 20; 30; 40; 50 m of the first drip line. Samples were collected in emitters located at the start, at 1/3, at 2/3 and at the end of the drip lines. The nutrient concentration was determined by flame spectrophotometry. The Christiansen's uniformity coefficients (CUC), of distribution (DUC), of statistical (SUC) and of emission (eUC) were estimated. The K2O concentration and distribution decreased linearly with the increase of the injection distance. In all treatments, the CUC, SUC and DUC were described as 'excellent'. The eUC was described as 'recommended' only at smaller injection distances.