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EN
This article describes the example of the vortical compressor using for synthesis-gas circulation in a methanol synthesis technological process. Application of a vortical compressor allows increase of productivity, decrease of power consumption and raise of energy efficiency factors of compressor for synthesis-gas circulation.
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Content available remote KINETIC CHARACTERISATION OF CATALYSTS FOR METHANOL SYNTHESIS
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The results of activity studies of four catalysts in methanol synthesis have been presented. A standard industrial catalyst TMC-3/1 was compared with two methanol catalysts promoted by the addition of magnesium and one promoted by zirconium. The kinetic analysis of the experimental results shows that the Cu/Zn/Al/Mg/1 catalyst was the least active. Although TMC-3/1 and Cu/Zn/Al/Mg/2 catalysts were characterised by a higher activity, the most active catalyst system was Cu/Zn/Al/Zr. The activity calculated for zirconium doped catalyst under operating conditions was approximately 30% higher that of TMC-3/1catalyst. The experimental data were used to identify the rate equations of two types - one purely empirical power rate equation and the other one - the Vanden Bussche & Froment kinetic model of methanol synthesis. The Cu/ZnO/Al2O3 catalyst modified with zirconium has the highest application potential in methanol synthesis.
EN
Effect of preparation method and substitution of Al2O3 by ZrO2 on the adsorption of CO, CO2, H2O and methanol on the Cu/ZnO/Al2O3 - ZrO2 catalysts as well as their activity in the synthesis of methanol from CO2 and H2 were investigated. The catalytic activity increases in the series: Cu/ZnO/Al2O3 obtained by co-precipitation < Cu/ZnO/Al2O3 < Cu/ZnO/Al2O3 - ZrO2 obtained by the amorphous precursor (citric acid) method < Cu/ZnO/ZrO2 obtained by the amorphous precursor (citric acid) method. It has been found that catalysts obtained by using citric acid as complexing agent show higher adsorption of methanol compared to water than the catalysts obtained by the coprecipitation. A partial substitution of Al2O3 by ZrO2 evidently decreases the reversible adsorption of water and CO. A correlation between adsorptive and catalytic properties has been established.With increasing ratio of reversibleCO2/CO orCH3OH/H2Oadsorption, an increase of the catalysts activity in the synthesis of methanol from CO2 and H2 is observed.
EN
The present work was a study on global reaction rate of methanol synthesis. We measured experimentally the global reaction rate in the internal recycle gradientless reactor over catalyst SC309. The diffusion-reaction model of methanol synthesis was suggested. For model we chose the hydrogenation of CO and CO2 &enspas key reaction. CO and CO2 &enspwere key components in our model. The internal diffusion effectiveness factors of CO and CO2&enspin the catalyst were calculated by the numerical integration. A comparison with the experiment showed that all the absolute values of the relative error were less than 10%. The simulation results showed that decreasing reaction temperature and catalyst diameter were conducive to reduce the influence of the internal diffusion on the methanol synthesis.
EN
The present work was a study on global reaction rate of methanol synthesis. We measured experimentally the global reaction rate in the internal recycle gradientless reactor over catalyst SC309. The diffusion-reaction model of methanol synthesis was suggested. For model we chose the hydrogenation of CO and CO2 as key reaction. CO and CO2 were key components in our model. The internal diffusion effectiveness factors of CO and CO2 in the catalyst were calculated by the numerical integration. A comparison with the experiment showed that all the absolute values of the relative error were less than 10%. The simulation results showed that decreasing reaction temperature and catalyst diameter were conducive to reduce the influence of the internal diffusion on the methanol synthesis.
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Content available remote COPPER/ZINC CATALYSTS IN HYDROGENATION OF CARBON OXIDES
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EN
Polish Academy of Sciences, Institute of Chemical Engineering, 44-100 Gliwice, Bałtycka 5, Poland A review concerning main processes of hydrogenation of carbon oxides towards synthesis of methanol, mixture of methanol and higher aliphatic alcohols and one-step synthesis of dimethyl ether as well as methanol steam reforming is given. Low-temperature methanol catalysts and lowtemperature modified methanol catalysts containing copper as primary component and zinc as secondary one are described.
EN
The aim of this work was to determine the correlation between catalytical activity of copper supported catalysts 60 per cent Cu/support (FeAlO3, ZnAl2O4) in methanol synthesis and their physicochemical properties. Surface area measurements (BET), X-ray diffraction (XRD) and temperature-programmed reduction (TPR-H2) techniques were used to study the physicochemical properties of Cu/support catalysts. The activity tests in methanol synthesis were carried out over copper catalysts in the temperature range 180–260 graduate C at elevated pressure (4 MPa) in a fixed bed reactor. Monometallic supported catalyst 60 per cent Cu/FeAlO3 was more active, but less selective in comparison with 60 per cent Cu/ZnAl2O4 catalyst in methanol synthesis. The XRD results confirmed the presence of binary oxide (ZnAl2O4 and FeAlO3), copper oxide, alfa-Fe2O3 and ZnO for appreciate copper supported catalysts. A reduction study of copper catalyst confirmed two step of copper oxide reduction (Cu2+ rightwards arrow Cu+rightwards arrow Cu0).
EN
In a continuing effort to realize the simultaneous hydrogen and methanol production via the auto-thermal methanol synthesis process, the effect of two different hydrogen redistribution strategies along a double-membrane reactor has been considered. A steady-state one-dimensional heterogeneous model was developed to compare two strategies applied in the operation of the auto-thermal methanol synthesis. It was found that the counter-current configuration exhibited the better performance compared to the reactor operated in the co-current mode from both the economic and environmental points of view. This superiority is ascribed to the establishment of a more favourable temperature profile along the reactor and also more hydrogen extraction from the reaction zone. Moreover, the influence of some operating variables was investigated on the performance of the auto-thermal double-membrane reactor in the counter-current configuration. The results suggest that utilizing this configuration for pure hydrogen and methanol production could be feasible and beneficial.
PL
Przeprowadzono badania wpływu promotorów Ce, Cr, Ga, La i Pd na aktywność katalizatora CuO/ZnO/ZrO2 w procesie syntezy metanolu z CO2 i H2. Katalizator otrzymano metodą homogenizacji z zastosowaniem kwasu cytrynowego wprowadzając niewielkie ilości promotorów. Aktywność katalizatorów badano prowadząc pomiary w ciśnieniowym reaktorze rurowym o stałym złożu katalizatora. Wykazano pozytywny wpływ promotorów, zwłaszcza Ga, La, Ce oraz Cr, na aktywność i selektywność katalizatora w badanym procesie.
EN
It has been well documented that the CuO/ZnO/ZrO2 catalyst shows high activity in the methanol synthesis from CO2 and H2. The CuO/ZnO/ZrO2 based catalysts were obtained by decomposing the citrate complexes, by adding small amount of promoters – Ce, Cr, Ga, La, Pd in order to improve the new catalyst’s catalytic properties. The catalytic activity was measured using a tubular high-pressure fixed bed reactor. The promoters were found to improve the catalytic activity and stability in the reaction of methanol synthesis from carbon dioxide and hydrogen. The positive influence of promoters, especially Ga, La, Ce and Cr on the activity and selectivity of the developed catalysts in the investigated process has been demonstrated.
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Content available remote Modelowanie syntezy metanolu w mikroreaktorze płytowym
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PL
W artykule przedstawiono wyniki symulacji numerycznej procesu syntezy metanolu z gazu syntezowego na katalizatorze Cu/ZnO/Al₂O₃ w reaktorze mikropłytowym. Zaprezentowano opis modelowy wymiany ciepła oraz masy syntezy metanolu w dwufazowym układzie gaz-ciało stałe z wykorzystaniem pseudojednorodnych modeli dyspersji. Do symulacji wykorzystano oprogramowanie COMSOL Multiphysics. Określono stopień konwersji CO oraz dezaktywacji katalizatora. Weryfikację wyników przeprowadzono w oparciu o prace literaturowe.
EN
This paper presents results of numerical simulation of the synthesis of methanol from syngas in plate microreactor over a catalyst Cu/ZnO/Al₂O₃. It presents a description of a model of heat transfer and mass of the methanol synthesis in a two phase gas-solid using pseudo-homogeneus dispersion models. The simulation used the software COMSOL Multiphysics. The conversion of CO and catalyst deactivation was described. Verification of the results was based on the works of literature.
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Content available remote Zgazowanie odpadów i synteza metanolu : analiza synergii procesów
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PL
Przedstawiono wyniki symulacji zgazowywania paliw alternatywnych, odpadów oraz węgla kamiennego. Przedstawiono bilans masowy konwersji CO i syntezy metanolu oraz analizowano koszty jego produkcji bez uwzględnienia nakładów inwestycyjnych oraz eksploatacyjnych instalacji. Dla procesu zgazowania i syntezy metanolu wybrano spośród analizowanych paliw rozwiązanie najbardziej korzystne w aspekcie surowcowym. Część projektowa obejmowała symulację procesu dla paliw przeznaczonyc do zastosowania w instalacji syntezy metanolu wykorzystującej gaz syntezowy jako surowiec. Opracowano koncepcyjny projekt instalacji oraz wykonano dla niej bilans masowy.
EN
Compn. of post-reaction gases produced by gasification of several alternative fuels and hard coal and conversions of the gases to MeOH were simulated by the Gumz and Traustel method. Temp., pressure and the nature of the gasification agent were selected as variables. Based on the data and prices of the gasifying agents, the MeOH prodn. costs were calcd. and compared to est. the optimal manufg. cost.
PL
W artykule rozwinięto koncepcję połączenia układu IGCC ze zgazowaniem węgla kamiennego w reaktorze ze złożem fluidalnym z jednoczesnym tlenowym spalaniem powstałego karbonizatu w kotle CFB na parametry nadkrytyczne. Celem pracy była ocena procesu energotechnologicznego wytwarzania gazu syntezowego do produkcji metanolu, skojarzonego z produkcją energii elektrycznej na potrzeby własne układu. Innowacyjność procesu polegała na zawróceniu części wytwarzanego CO2 i wykorzystania go w procesie zgazowania, a także dopalania powstałego w procesie zgazowania karbonizatu z wykorzystaniem technologii spalania tlenowego. Obliczenia symulacyjne przeprowadzono przy założeniu zastosowania technologii usuwania CO2 metodą aminową oraz bez niej. Podziału obciążeń środowiskowych towarzyszących rozważanemu procesowi (jednostkowe zużycie energii i emisja CO2) dokonano przy zastosowaniu metody unikniętych nakładów paliwowych.
EN
The article develops the idea of integration of CFB reactor based IGCC system and oxy-combustion of char in a supercritical CFB boiler. The aim of this paper is to analyze the operation of an energotechnological system aimed at production of for methanol synthesis and electricity. The innovation aspect of the system is the recirculation of major amount of produced CO2 and its dual application as gasification agent and oxygen diluting medium before oxy-combustion. The simulation was performed for two variants of the proposed system: with and without CO2 capture based on amine absorption technology. Allocation of environmental burdens (unit energy consumption and CO2 emission) was done basing on the avoided fuel input idea.
PL
W artykule przybliżono reakcję syntezy niskocząsteczkowych alkoholi z mieszaniny tlenków węgla oraz wodoru. Na podstawie dostępnych danych literaturowych przedstawiono typowe warunki prowadzenia procesu oraz stosowane katalizatory. Ponadto omówiono podstawy termodynamiki procesu oraz możliwe ścieżki mechanizmu.
EN
The paper discusses the reaction of lower alcohol synthesis from mixture of carbon oxides and hydrogen. From available literature data the typical processing conditions and applied catalysts were presented. Moreover, the most important thermodynamic relations and possible mechanisms were also discussed.
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The results of activity studies of four catalysts in methanol synthesis have been presented. A standard industrial catalyst TMC-3/1 was compared with two methanol catalysts promoted by the addition of magnesium and one promoted by zirconium. The kinetic analysis of the experimental results shows that the Cu/Zn/Al/Mg/1 catalyst was the least active. Although TMC-3/1 and Cu/Zn/Al/Mg/2 catalysts were characterised by a higher activity, the most active catalyst system was Cu/Zn/Al/Zr. The activity calculated for zirconium doped catalyst under operating conditions was approximately 30% higher that of TMC-3/1catalyst. The experimental data were used to identify the rate equations of two types – one purely empirical power rate equation and the other one - the Vanden Bussche & Froment kinetic model of methanol synthesis. The Cu/ZnO/Al2O3catalyst modified with zirconium has the highest application potential in methanol synthesis.
EN
The influence of copper and noble metal (Ag, Au) addition on the physicochemical properties of support FeAlO3 and supported metal catalysts was studied. The reaction of methanol formation in the temperature range 200-380 graduate C under atmospheric pressure over a series of Cu and M-Cu catalysts (where M = Ag, Au) has been investigated. The presence of spinel like type structures FeAlO3, Fe2AlO4 and FeAl2O4 was confirmed by XRD technique. The physicochemical properties of supports and supported copper and bimetallic Ag, Au-Cu/FeAlO3 catalysts were examined by BET, TPR, and XRD methods.
PL
W ramach dążenia do wykorzystania nadmiaru emitowanego ditlenku węgla, opracowano nowoczesny katalizator Cu/Zn/Zr modyfikowany Ce, Cr, Ga lub ich mieszaniną do produkcji metanolu z gazu bogatego w ditlenek węgla. Stwierdzono, że wprowadzone dodatki pozytywnie wpływają na aktywność wytworzonych katalizatorów w badanym procesie. Badania prowadzono w reaktorze rurowym ze stałym złożem katalizatora, w zakresie temp. 443–513 K, pod ciśnieniem 8 MPa. Najlepszym katalizatorem okazał się Cu/Zn/Zr/Ga. Charakteryzuje się on dużą stabilnością osiągając wysoką, przekraczającą 200 g/(kg·h) wydajność metanolu, przy 70% selektywności w kierunku tworzenia metanolu w temp. 513 K.
EN
Eight Cu/Zn/Zr catalysts were modified with Ce, Cr or their mixts., then characterized and used for MeOH synthesis in a tubular fixed-bed reactor at 443–513 K under 8 MPa. The highest yield (200 g/(kg∙h)) and selectivity to methanol (70%) was achived for Cu/Zn/Zr/Ga catalyst.
PL
Sporządzono numeryczny model wytwórni metanolu z gazu syntezowego. Przeanalizowano wariant oczyszczania gazu syntezowego ze składników kwaśnych w celu dostosowania jego wymagań jakościowych do syntezy metanolu. Omówiono aspekty technologiczne wytwórni dotyczące ograniczeń procesowych. Na podstawie sporządzonych bilansów masowo-energetycznych określono sprawność całego procesu wraz ze zużyciem energii elektrycznej. Wykonano obliczenia numeryczne nad syntezą metanolu z wykorzystaniem modeli kinetycznych Kliera oraz Šetinca i Leveca. Przeprowadzone analizy procesowe stanowią dane wejściowe zarówno w badaniach nad optymalizacją procesu, jak i przy obliczeniach związanych z projektem instalacji technologicznej.
EN
MeOH synthesis by conversion of syngas on suspended CuO/ZnO/Al2O3 catalyst was modelled to est. the process balances and kinetics and to optimize the process conditions and its energy efficiency. The Klier and Šetinc-Levec kinetic models were used for numerical calcns.
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Content available remote Węgiel kamienny jako surowiec do produkcji paliw płynnych w Polsce
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A review concerning main processes of hydrogenation of carbon oxides towards synthesis of methanol, mixture of methanol and higher aliphatic alcohols and one-step synthesis of dimethyl ether as well as methanol steam reforming is given. Low-temperature methanol catalysts and low-temperature modified methanol catalysts containing copper as primary component and zinc as secondary one are described.
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