946 resultados para GAS-LIQUID FLOW


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The role of busulfan (Bu) metabolites in the adverse events seen during hematopoietic stem cell transplantation and in drug interactions is not explored. Lack of availability of established analytical methods limits our understanding in this area. The present work describes a novel gas chromatography-tandem mass spectrometric assay for the analysis of sulfolane (Su) in plasma of patients receiving high-dose Bu. Su and Bu were extracted from a single 100 μL plasma sample by liquid-liquid extraction. Bu was separately derivatized with 2,3,5,6-tetrafluorothiophenolfluorinated agent. Mass spectrometric detection of the analytes was performed in the selected reaction monitoring mode on a triple quadrupole instrument after electronic impact ionization. Bu and Su were analyzed with separate chromatographic programs, lasting 5 min each. The assay for Su was found to be linear in the concentration range of 20-400 ng/mL. The method has satisfactory sensitivity (lower limit of quantification, 20 ng/mL) and precision (relative standard deviation less than 15 %) for all the concentrations tested with a good trueness (100 ± 5 %). This method was applied to measure Su from pediatric patients with samples collected 4 h after dose 1 (n = 46), before dose 7 (n = 56), and after dose 9 (n = 54) infusions of Bu. Su (mean ± SD) was detectable in plasma of patients 4 h after dose 1, and higher levels were observed after dose 9 (249.9 ± 123.4 ng/mL). This method may be used in clinical studies investigating the role of Su on adverse events and drug interactions associated with Bu therapy.

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A gas chromatographic-mass spectrometric (GC-MS) method has been developed, for the determination of trimipramine (TRI), desmethyltrimipramine (DTRI), didesmethyltrimipramine (DDTRI), 2-hydroxytrimipramine (2-OH-TRI) and 2-hydroxydesmethyltrimipramine (2-OH-DTRI). The method includes two derivatization steps with trifluoroacetic acid anhydride and N-methyl-N-(tert.-butyldimethyl silyl)trifluoroacetamide and the use of an SE-54 capillary silica column. The limits of quantitation were found to be 2 ng/ml for DTRI and 4 ng/ml for all other substances. Besides, methods have been optimized for the hydrolysis of the glucuronic acid conjugated metabolites. This specific detection method is useful, as polymedication is a usual practice in clinical situations, and its sensitivity allows its use for single-dose pharmacokinetic studies.

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In this article, selected examples of applications of liquid chromatography coupled to mass spectrometry are given. The examples include the analysis of i) impurities in manufactured, pharmaceutical or synthesis products, ii) polyphenols in natural products, and iii) phytohormones in plant extracts. Finally, examples of applications of molecular characterization via flow injection analysis by electron spray ionization mass spectrometry (ESI-MS) are also given.

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Capillary electrophoresis has drawn considerable attention in the past few years, particularly in the field of chiral separations because of its high separation efficiency. However, its routine use in therapeutic drug monitoring is hampered by its low sensitivity due to a short optical path. We have developed a capillary zone electrophoresis (CZE) method using 2mM of hydroxypropyl-β-cyclodextrin as a chiral selector, which allows base-to-base separation of the enantiomers of mianserin (MIA), desmethylmianserin (DMIA), and 8-hydroxymianserin (OHMIA). Through the use of an on-column sample concentration step after liquid-liquid extraction from plasma and through the presence of an internal standard, the quantitation limits were found to be 5 ng/mL for each enantiomer of MIA and DMIA and 15 ng/mL for each enantiomer of OHMIA. To our knowledge, this is the first published CE method that allows its use for therapeutic monitoring of antidepressants due to its sensitivity down to the low nanogram range. The variability of the assays, as assessed by the coefficients of variation (CV) measured at two concentrations for each substance, ranged from 2 to 14% for the intraday (eight replicates) and from 5 to 14% for the interday (eight replicates) experiments. The deviations from the theoretical concentrations, which represent the accuracy of the method, were all within 12.5%. A linear response was obtained for all compounds within the range of concentrations used for the calibration curves (10-150 ng/mL for each enantiomer of MIA and DMIA and 20-300 ng/mL for each enantiomer of OHMIA). Good correlations were calculated between [(R) + (S)]-MIA and DMIA concentrations measured in plasma samples of 20 patients by a nonchiral gas chromatography method and CZE, and between the (R)- and (S)-concentrations of MIA and DMIA measured in plasma samples of 37 patients by a previously described chiral high-performance liquid chromatography method and CZE. Finally, no interference was noted from more than 20 other psychotropic drugs. Thus, this method, which is both sensitive and selective, can be routinely used for therapeutic monitoring of the enantiomers of MIA and its metabolites. It could be very useful due to the demonstrated interindividual variability of the stereoselective metabolism of MIA.

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New methodologies for the analysis of volatile compoundsusing needle traps. Applications to breath, atmospheric andwater analysis. A new preconcentration technique has been developed for the analysis of volatile compounds based on the use of needle traps. These traps are based on stainless steel needles filled with one or more adsorbents, which allows the preconcentration of the anilities inside the trap by passing a gas flow through the needle. The parameters affecting the sorption/desorption process have been assessed (e.g. needle and liner dimensions, injector temperature, split less time, memory effects, and stability inside the needle). For liquid samples, four different sampling methodologies were studied, including passive and active sampling methods. The best results, considering the simplicity and sensitivity, are obtained by sampling the headspace volume using various cycles of a small and fix volume. Once the best conditions of analysis have been found, the method has been validated for gas and liquid samples. The results obtained show that needle traps are a good analytical methodology for the analysis of breath, environmental and liquid samples

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Granular flow phenomena are frequently encountered in the design of process and industrial plants in the traditional fields of the chemical, nuclear and oil industries as well as in other activities such as food and materials handling. Multi-phase flow is one important branch of the granular flow. Granular materials have unusual kinds of behavior compared to normal materials, either solids or fluids. Although some of the characteristics are still not well-known yet, one thing is confirmed: the particle-particle interaction plays a key role in the dynamics of granular materials, especially for dense granular materials. At the beginning of this thesis, detailed illustration of developing two models for describing the interaction based on the results of finite-element simulation, dimension analysis and numerical simulation is presented. The first model is used to describing the normal collision of viscoelastic particles. Based on some existent models, more parameters are added to this model, which make the model predict the experimental results more accurately. The second model is used for oblique collision, which include the effects from tangential velocity, angular velocity and surface friction based on Coulomb's law. The theoretical predictions of this model are in agreement with those by finite-element simulation. I n the latter chapters of this thesis, the models are used to predict industrial granular flow and the agreement between the simulations and experiments also shows the validation of the new model. The first case presents the simulation of granular flow passing over a circular obstacle. The simulations successfully predict the existence of a parabolic steady layer and show how the characteristics of the particles, such as coefficients of restitution and surface friction affect the separation results. The second case is a spinning container filled with granular material. Employing the previous models, the simulation could also reproduce experimentally observed phenomena, such as a depression in the center of a high frequency rotation. The third application is about gas-solid mixed flow in a vertically vibrated device. Gas phase motion is added to coherence with the particle motion. The governing equations of the gas phase are solved by using the Large eddy simulation (LES) and particle motion is predicted by using the Lagrangian method. The simulation predicted some pattern formation reported by experiment.

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Centrifugal compressors are widely used for example in process industry, oil and gas industry, in small gas turbines and turbochargers. In order to achieve lower consumption of energy and operation costs the efficiency of the compressor needs to be improve. In the present work different pinches and low solidity vaned diffusers were utilized in order to improve the efficiency of a medium size centrifugal compressor. In this study, pinch means the decrement of the diffuser flow passage height. First different geometries were analyzed using computational fluid dynamics. The flow solver Finflo was used to solve the flow field. Finflo is a Navier-Stokes solver. The solver is capable to solve compressible, incompressible, steady and unsteady flow fields. Chien's k-e turbulence model was used. One of the numerically investigated pinched diffuser and one low solidity vaned diffuser were studied experimentally. The overall performance of the compressor and the static pressure distribution before and after the diffuser were measured. The flow entering and leaving the diffuser was measured using a three-hole Cobra-probe and Kiel-probes. The pinch and the low solidity vaned diffuser increased the efficiency of the compressor. Highest isentropic efficiency increment obtained was 3\% of the design isentropic efficiency of the original geometry. It was noticed in the numerical results that the pinch made to the hub and the shroud wall was most beneficial to the operation of the compressor. Also the pinch made to the hub was better than the pinchmade to the shroud. The pinch did not affect the operation range of the compressor, but the low solidity vaned diffuser slightly decreased the operation range.The unsteady phenomena in the vaneless diffuser were studied experimentally andnumerically. The unsteady static pressure was measured at the diffuser inlet and outlet, and time-accurate numerical simulation was conducted. The unsteady static pressure showed that most of the pressure variations lay at the passing frequency of every second blade. The pressure variations did not vanish in the diffuser and were visible at the diffuser outlet. However, the amplitude of the pressure variations decreased in the diffuser. The time-accurate calculations showed quite a good agreement with the measured data. Agreement was very good at the design operation point, even though the computational grid was not dense enough inthe volute and in the exit cone. The time-accurate calculation over-predicted the amplitude of the pressure variations at high flow.

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A highly sensitive ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) method was developed for the quantification of buprenorphine and its major metabolite norbuprenorphine in human plasma. In order to speed up the process and decrease costs, sample preparation was performed by simple protein precipitation with acetonitrile. To the best of our knowledge, this is the first application of this extraction technique for the quantification of buprenorphine in plasma. Matrix effects were strongly reduced and selectivity increased by using an efficient chromatographic separation on a sub-2μm column (Acquity UPLC BEH C18 1.7μm, 2.1×50mm) in 5min with a gradient of ammonium formate 20mM pH 3.05 and acetonitrile as mobile phase at a flow rate of 0.4ml/min. Detection was made using a tandem quadrupole mass spectrometer operating in positive electrospray ionization mode, using multiple reaction monitoring. The procedure was fully validated according to the latest Food and Drug Administration guidelines and the Société Française des Sciences et Techniques Pharmaceutiques. Very good results were obtained by using a stable isotope-labeled internal standard for each analyte, to compensate for the variability due to the extraction and ionization steps. The method was very sensitive with lower limits of quantification of 0.1ng/ml for buprenorphine and 0.25ng/ml for norbuprenorphine. The upper limit of quantification was 250ng/ml for both drugs. Trueness (98.4-113.7%), repeatability (1.9-7.7%), intermediate precision (2.6-7.9%) and internal standard-normalized matrix effects (94-101%) were in accordance with international recommendations. The procedure was successfully used to quantify plasma samples from patients included in a clinical pharmacogenetic study and can be transferred for routine therapeutic drug monitoring in clinical laboratories without further development.

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The present work describes a fast gas chromatography/negative-ion chemical ionization tandem mass spectrometric assay (Fast GC/NICI-MS/MS) for analysis of tetrahydrocannabinol (THC), 11-hydroxy-tetrahydrocannabinol (THC-OH) and 11-nor-9-carboxy-tetrahydrocannabinol (THC-COOH) in whole blood. The cannabinoids were extracted from 500 microL of whole blood by a simple liquid-liquid extraction (LLE) and then derivatized by using trifluoroacetic anhydride (TFAA) and hexafluoro-2-propanol (HFIP) as fluorinated agents. Mass spectrometric detection of the analytes was performed in the selected reaction-monitoring mode on a triple quadrupole instrument after negative-ion chemical ionization. The assay was found to be linear in the concentration range of 0.5-20 ng/mL for THC and THC-OH, and of 2.5-100 ng/mL for THC-COOH. Repeatability and intermediate precision were found less than 12% for all concentrations tested. Under standard chromatographic conditions, the run cycle time would have been 15 min. By using fast conditions of separation, the assay analysis time has been reduced to 5 min, without compromising the chromatographic resolution. Finally, a simple approach for estimating the uncertainty measurement is presented.

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The studies of flow phenomena, heat and mass transfer in microchannel reactors are beneficial to estimate and evaluate the ability of microchannel reactors to be operated for a given process reaction such as Fischer-Tropsch synthesis. The flow phenomena, for example, the flow regimes and flow patterns in microchannel reactors for both single phase and multiphase flow are affected by the configuration of the flow channel. The reviews of the previous works about the analysis of related parameters that affect the flow phenomena are shown in this report. In order to predict the phenomena of Fischer-Tropsch synthesis in microchannel reactors, the 3-dimensional computational fluid dynamic simulation with commercial software package FLUENT was done to study the flow phenomena and heat transfer for gas phase Fischer-Tropsch products flow in rectangular microchannel with hydraulic diameter 500 ¿m and length 15 cm. Numerical solution with slip boundary condition was used in the simulation and the flowphenomena and heat transfer were determined.

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This study considered the current situation of solid and liquid biofuels markets and international biofuels trade in Finland and identified the challenges ofthe emerging international biofuels markets for Finland. The fact that industryconsumes more than half of the total primary energy, widely applied combined heat and power production (CHP) and a high share of biofuels in the total energy consumption are specific to the Finnish energy system. One third of the electricity is generated in CHP plants. As much as 27% of the total energy consumption ismet by using wood and peat, which makes Finland the leading country in the use of biofuels. Finland has made a commitment to maintain greenhouse gas emissions at the 1990 level at the highest during the period 2008-2012. The Finnish energypolicy aims to achieve the target, and a variety of measures are taken to promote the use of renewable energy sources and especially wood fuels. In this study, the wooden raw material streams of the forest industry were included the international biofuels trade in addition to biomass streams that are traded for energy production. In 2004, as much as 45% of the raw wood importedinto Finland ended up in energy production. The total international trading of biofuels was evaluated at 72 PJ, of which the majority, 58 PJ, was raw wood. About 22% of wood based energy in Finland originated from imported raw wood. Tall oil and wood pellets composed the largest export streams of biofuels. The annual turnover of international biofuels trade was estimated at about ¤ 90 million fordirect trade and at about ¤ 190 million for indirect trade. The forest industryas the biggest user of wood, and the producer and user of wood fuels has a central position in biomass and biofuels markets in Finland. Lately, the international aspects of Finnish biofuels markets have been emphasised as the import of rawwood and the export of wood pellets have increased. Expanding the use of biofuels in the road transportation sector would increase the international streams ofbiofuels in Finland. In coming years, the international trading of biomass for energy purposes can be expected to continue growing.

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Woven monofilament, multifilament, and spun yarn filter media have long been the standard media in liquid filtration equipment. While the energy for a solid-liquid separation process is determined by the engineering work, it is the interface between the slurry and the equipment - the filter media - that greatly affects the performance characteristics of the unit operation. Those skilled in the art are well aware that a poorly designed filter medium may endanger the whole operation, whereas well-performing filter media can make the operation smooth and economical. As the mineral and pulp producers seek to produce ever finer and more refined fractions of their products, it is becoming increasingly important to be able to dewater slurries with average particle sizes around 1 ¿m using conventional, high-capacity filtration equipment. Furthermore, the surface properties of the media must not allow sticky and adhesive particles to adhere to the media. The aim of this thesis was to test how the dirt-repellency, electrical resistance and highpressure filtration performance of selected woven filter media can be improved by modifying the fabric or yarn with coating, chemical treatment and calendering. The results achieved by chemical surface treatments clearly show that the woven media surface properties can be modified to achieve lower electrical resistance and improved dirt-repellency. The main challenge with the chemical treatments is the abrasion resistance and, while the experimental results indicate that the treatment is sufficiently permanent to resist standard weathering conditions, they may still prove to be inadequately strong in terms of actual use.From the pressure filtration studies in this work, it seems obvious that the conventional woven multifilament fabrics still perform surprisingly well against the coated media in terms of filtrate clarity and cake build-up. Especially in cases where the feed slurry concentration was low and the pressures moderate, the conventional media seemed to outperform the coated media. In the cases where thefeed slurry concentration was high, the tightly woven media performed well against the monofilament reference fabrics, but seemed to do worse than some of the coated media. This result is somewhat surprising in that the high initial specific resistance of the coated media would suggest that the media will blind more easily than the plain woven media. The results indicate, however, that it is actually the woven media that gradually clogs during the coarse of filtration. In conclusion, it seems obvious that there is a pressure limit above which the woven media looses its capacity to keep the solid particles from penetrating the structure. This finding suggests that for extreme pressures the only foreseeable solution is the coated fabrics supported by a strong enough woven fabric to hold thestructure together. Having said that, the high pressure filtration process seems to follow somewhat different laws than the more conventional processes. Based on the results, it may well be that the role of the cloth is most of all to support the cake, and the main performance-determining factor is a long life time. Measuring the pore size distribution with a commercially available porometer gives a fairly accurate picture of the pore size distribution of a fabric, but failsto give insight into which of the pore sizes is the most important in determining the flow through the fabric. Historically air, and sometimes water, permeability measures have been the standard in evaluating media filtration performance including particle retention. Permeability, however, is a function of a multitudeof variables and does not directly allow the estimation of the effective pore size. In this study a new method for estimating the effective pore size and open pore area in a densely woven multifilament fabric was developed. The method combines a simplified equation of the electrical resistance of fabric with the Hagen-Poiseuille flow equation to estimate the effective pore size of a fabric and the total open area of pores. The results are validated by comparison to the measured values of the largest pore size (Bubble point) and the average pore size. The results show good correlation with measured values. However, the measured and estimated values tend to diverge in high weft density fabrics. This phenomenon is thought to be a result of a more tortuous flow path of denser fabrics, and could most probably be cured by using another value for the tortuosity factor.

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A rigorous unit operation model is developed for vapor membrane separation. The new model is able to describe temperature, pressure, and concentration dependent permeation as wellreal fluid effects in vapor and gas separation with hydrocarbon selective rubbery polymeric membranes. The permeation through the membrane is described by a separate treatment of sorption and diffusion within the membrane. The chemical engineering thermodynamics is used to describe the equilibrium sorption of vapors and gases in rubbery membranes with equation of state models for polymeric systems. Also a new modification of the UNIFAC model is proposed for this purpose. Various thermodynamic models are extensively compared in order to verify the models' ability to predict and correlate experimental vapor-liquid equilibrium data. The penetrant transport through the selective layer of the membrane is described with the generalized Maxwell-Stefan equations, which are able to account for thebulk flux contribution as well as the diffusive coupling effect. A method is described to compute and correlate binary penetrant¿membrane diffusion coefficients from the experimental permeability coefficients at different temperatures and pressures. A fluid flow model for spiral-wound modules is derived from the conservation equation of mass, momentum, and energy. The conservation equations are presented in a discretized form by using the control volume approach. A combination of the permeation model and the fluid flow model yields the desired rigorous model for vapor membrane separation. The model is implemented into an inhouse process simulator and so vapor membrane separation may be evaluated as an integralpart of a process flowsheet.

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Työssä tutkittiin uutta teknologiaa pigmenttipäällystykseen. Tämä tekniikka on yleisesti tunnettua eräillä muilla teollisuudenaloilla. Kirjallisuustutkimuksessa on esitelty prosessia ja sen eri osatekijöitä sekä muilla aloilla tunnettuja prosessimuuttujia. Päällystyspastojen ja päällystettävien pintojen teoriaa on selvitetty uuden tekniikan ja pigmenttipäällystyksen valossa. Uuden tekniikan perusmekanismeja tutkittiin kokeellisessa osassa. Valuvan nestefilmin stabiilisuutta tutkittiin minimivirtauksen avulla. Stabiilisuustutkimuksen suorittamiseen käytettiin apuna Taguchi-matriisia DOE-ohjelmalla (Design of Experiments). Kokeiden perusteella minimivirtauksen kannalta päällystyspastalle edullisempi koostumus on kalsiumkarbonaatti- kuin kaoliinipasta. Sideaineella on pienempi osuus lateksia ja polyvinyylialkoholia parempi. Suurempi osuus pinta-aktiivista ainetta ja matala pastan kuiva-ainepitoisuus ovat suositeltuja. Tehokas ilmanpoisto päällystyspastasta on myös tärkeää lopullisen tuloksen kannalta. Koekoneella ajetuissa päällystyskokeissa havaittiin valuvan filmin ominaisuuksien tärkeys. Pienetkin kaasumäärät päällystyspastassa häiritsivät lopullisen päällysteen laatua. Päällystyspastan ilmanpoisto on avainasemassa erityisesti kun päällystetään suurella nopeudella pieniä päällystemääriä. Koeajoissa havaittiin kaikki kirjallisuudessa esitellyt rajoittavat tekijät. Kokeissa päällystettiin 400-1600 m/min nopeudella 5-20 g/m² päällystemääriä. Olosuhteet stabiilille nestefilmille vaativat edelleen kehitystä suurella nopeudella päällystettäessä. Päällysteen eroavaisuuksia verrattiin teräpäällystysmenetelmiin. Terä-päällystyksellä saadaan sileä mutta epätasaisesti peittävä pinta kun taas uuden tekniikan päällyste mukailee päällystettävän alustan topografiaa. Tasapaksun päällysteen etuna on hyvä peittävyys jo pienellä päällystemäärällä.

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Tässä työssä selostetaan kuumalanka-anemometrin käyttö virtausmittauksissa. Kuumalanka-anemometrilla saadaan mitattua virtausnopeuden ja -suunnan lisäksi nopeusheilahteluja. Mittaustaajuus on tyypillisesti useita kymmeniä tuhansia mittauksia sekunnissa ja signaali on jatkuva. Nykytekniikalla pystytään helposti tallentamaan mittauslaitteistolta saatu viesti tietokoneelle ja muuntamaan se nopeudeksi. Hetkellisten nopeuksien avulla voidaan laskea turbulenttisen virtauksen ominaisuuksia, kuten turbulenssin intensiteetti ja spektri. Kuumalanka-anemometrissa lämmitetään sähköisesti ohutta lankaa, joka on mitattavassa virtauksessa. Langan sähköteho on suunnilleen yhtäsuuri kuin langasta konvektiolla siirtyvä lämpöteho. Tällöin on teoreettisesti mahdollista laskea virtausnopeus lämpötehosta lämmönsiirtokorrelaatioilla. Käytännössä laitteisto joudutaan kuitenkin erikseen kalibroimaan, mutta sähkötehon teoreettista riippuvuutta konvektiosta käytetään hyväksi. Kuumalangan lämmitettävä osuus on tyypillisesti halkaisijaltaan 5 µm ja pituudeltaan noin 1 mm. Sitä käytetään pääasiassa kaasuvirtausten mittaamiseen ja valtaosassa mittauksissa virtausaineena on ilma. Kuumalanka voi olla toteutettu kuumakalvotekniikalla, jossa halkaisijaltaan noin 50 - 70 µm paksuinen kuitu on päällystetty ohuella sähköä johtavalla kalvolla. Kuumakalvoanturin ei tarvitse olla muodoltaan sylinterimäinen, se voi olla mm. kartiomainen tai kiilamainen. Erikoispäällystetyllä kuumakalvoanturilla on mahdollista mitata myös nestevirtauksia. Mitattaessa kaasuvirtauksia kuumakalvon etuna on selvästi parempi kestävyys verrattuna kuumalankaan. Nimitystä kuumalanka-anemometri käytetään yleisesti molemmista anturityypeistä Tämän työn alussa käsitellään sylinterin yli tapahtuvaan virtaukseen liittyvää virtausmekaniikkaa ja lämmönsiirtoa. Anemometrin sähköinen osa, laitteisto ja sen kalibrointi käydään läpi. Langan suuntariippuvuuden laskentaan esitetään tarvittavat yhtälöt. Työssä esitellään kolme laitteistolla tehtyä perusmittausta: anturin kohtauskulman muuttaminen, pyörähdyssymmerisen suihkun nopeuskenttä ja tuulitunnelin rajakerros. Lisäksi esitellään yksi käytännöllinen ja vaativampi mittaus, jossa on mitattu nopeusprofiili radiaalikompressorin diffuusorin loppuosassa.