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EN
The reforming of methane with carbon dioxide is still of great interest due to the ever-increasing demand for synthesis gas and hydrogen. This process makes it possible to use two major gases that are considered harmful to the environment. The main problem for its commercial application is the lack of a catalyst that is both active, selective towards syngas (a mixture of hydrogen and carbon monoxide) and resistant to deactivation by coke deposition. Nickel is the most commonly used metal in methane reforming reactions due to its high activity and reasonable price. But still there is a gap in the literature for research on novel catalysts and their properties modifications devoted to strategies to reduce deactivation of the catalysts caused by the coke formation. In the present work a series of hydroxyapatite supported nickel catalysts promoted by alkali metals (Li, Na, K and Cs) were tested. The surface and structural properties of the catalysts were well characterized by physicochemical methods. Activity and selectivity were measured at 600ºC for 20 hours’ time-on-stream test. Resistance to coking was measured with Magnetic Suspension Balance. The stability of the catalyst was improved by the addition of promoters, which reduced the rate of coking. In particular, the cesium-promoted Ni/HAp catalyst significantly inhibited coke deposition, while slightly reducing methane conversion and selectivity to hydrogen.
PL
Katalizatory wykorzystywane w procesie reformingu parowego pomimo możliwości wielokrotnej ich regeneracji ulegają zużyciu i muszą zostać wymienione na nowe. Składowanie zużytych katalizatorów zawierających osadzone na nośniku ceramicznym związki niklu może doprowadzić do skażenia środowiska tym metalem oraz innymi metalami ciężkimi wchodzącymi w skład katalizatora. Zagrożenie to wielokrotnie maleje w przypadku uprzedniego usunięcia niklu z nośnika przez wymycie mocnymi kwasami nieorganicznymi. Zaprezentowano wyniki badań dotyczących zawartości niklu w zużytym katalizatorze G-0110 oraz w zużytym katalizatorze G-0110 poddanym ługowaniu kwasem chlorowodorowym o stężeniu 3 mol/L. Nikiel ekstrahowano do fazy ciekłej w warunkach opisanych w procedurze ekstrakcji sekwencyjnej BCR.
EN
The spent Ni catalyst from the 2nd stage steam reforming and the catalyst previously leached with 3 mol/L HCl were sequential extd. to det. the content of Ni, Co, Cd, Cr, Pb and Mn and to det. the form in which they occur. The metal content in the solns. was detd. by atomic absorption spectrometry (FAAS or GFAAS), and in the catalysts by X- ray diffraction (XRD) and X-ray photoelectron spectrometry (XPS). Sequential extn. allowed to ext. significant amts. of Ni contained in the catalyst. Leaching of the catalyst with 3 mol/L HCl led to a redn. in the total content of all tested elements in the material. The highest degree of leaching was found for Ni (98.4%), and the lowest for Pb (20.7%) and Cd (17.1%).
EN
Tar formation is a significant issue during biomass gasification. Catalytic removal of tars with the use of nickel cata-lyst allows to obtain high conversion rate but coke formation on catalysts surface lead to its deactivation. Toluene decomposition as a tar imitator was studied in gliding discharge plasma-catalytic system with the use of 5%, 10% and 15% by weight Ni and NiO catalyst on Al2O3 (α-Al2O3) and Peshiney (γ-Al2O3) carrier in gas composition similar to the gas after biomass pyrolysis. The optimal concentration of nickel was identified to be 10% by weight on Al2O3. It was stable in all studiedinitial toluene concentrations, discharge power while C7H8 conversion rate remained high – up to 82%. During the process, nickel catalysts were deactivated by sooth formation on the surface. On catalysts surface, toluene decomposition products were identified including benzyl alcohol and 3-hexen-2-one.
EN
This paper presents the results of investigations into dry methane reforming (DMR). The process was aimed at obtaining synthesis gas required for the production of dimethyl ether (DME). The effect of temperature, pressure and inlet gas composition on the process was determined in the experimental part of this work. The tests were carried out in a laboratory tubular reactor over a Ni/CaO–Al2O3 catalyst. The obtained experimental results were used to verify literature kinetic data and to develop a mathematical model of the DMR process.
EN
In order to produce valuable syngas, industrial processes of dry reforming of methane and steam reforming of methane must be further developed. This paper is focused on reviewing recently examined catalysts, supporting the mentioned technologies. In both processes the most popular active material choice is usually nickel, due to its good availability. On the other hand, noble metals, such as ruthenium, rhodium or platinum, provide better performance, however the solution is not cost-effective. Materials used as a support influence the catalytic activity. Oxides with basic properties, such as MgO, Al2 O3 , CeO2 , are frequently used as carriers. One of the most promising materials for reforming of methane technologies are hydrotalcites, due to adjustable composition, acid-base properties and possibility of incorporation of various metals and complexes.
6
Content available remote Wpływ składu stopu Raneya na aktywność niklowego katalizatora szkieletowego
PL
Przeanalizowano wpływ składu stopu Raneya, otrzymanego przez stopienie aluminium i niklu występujących w różnych proporcjach masowych, z którego aluminium zostaje wymyte alkaliami, a nikiel pozostaje w postaci rozdrobnionej, na aktywność niklowego katalizatora szkieletowego w procesie uwodornienia kwasu maleinowego do kwasu bursztynowego. Jest to uzupełnienie wcześniejszych badań przeprowadzonych na szkieletowym katalizatorze niklowym, uzyskanym ze stopu Raneya otrzymanego przez stopienie równych mas aluminium i niklu, prezentowanych w pracy1). Wykazano, że wzrost zawartości aluminium w stopie zwiększa aktywność niklowego katalizatora w analizowanym procesie.
EN
Ni-Al alloys were prepd. by smelting the components, annealed at 600–1250°C, leached with aq. NaOH soln. at 80– 100°C and then tested for catalytic activity in hydrogenation of maleic acid. The increase in the Ni:Al mass ratio resulted in a decrease both in the activity of the catalyst and in the initial electrochem. potential value of the indicator electrode.
PL
Przedstawiono wyniki badań fizykochemicznych właściwości dwóch prekursorów katalizatora do utwardzania tłuszczów: niklowo-glinowego oraz niklowo-glinowego z dodatkiem ceru. Zbadano wpływ dodatku ceru na aktywność katalizatora Ni/(Al2O3•CeO2) w procesie uwodornienia bielonego oleju rzepakowego oraz na ilość powstających izomerów trans kwasów tłuszczowych w uwodornionym produkcie.
EN
Two Ni/Al2O3 and Ni/(Al2O3•CeO2) catalysts were prepd. and used for hydrogenation of bleached rapeseed oil in a batch reactor at 180ºC under 1.5-20 atm. The addn. of Ce resulted in decreasing the content of trans-fatty acids in the product of the reaction carried out under 20 atm.
PL
Przedstawiono wyniki badania uwodornienia kwasów tłuszczowych, prowadzonego metodą okresową, w obecności katalizatora niklowego zawieszonego w cieczy. Określono wpływ temperatury, ciśnienia, stężenia katalizatora i czasu reakcji na liczbę jodową stearyny. Stwierdzono, że największy wpływ na liczbę jodową uwodornionych kwasów tłuszczowych ma stężenie katalizatora. Dobór opracowanych parametrów pozwala na otrzymanie produktu o wymaganej dla stearyny liczbie jodowej mniejszej od 1 przy czasie reakcji do 60 min.
EN
Stearin is a mixt. of solid fatty acids, mainly stearic and palmitic. Distd. animal fats contg. monoglycerides 0.4, satd. and unsatd. fatty acids 47.4 and 52.2%, resp. , acid and sapn. nos. resp. 203.9 and 205.5 mg KOH/g, I no. 55.9 g/100 g, and m.p. 39°C, were hydrogenated over a Ni catalyst, 3–5 mm flakes, bulk d. 0.85, contg. Ni 20, aluminosilicates 10, and hardened fat 70%, sp. surface 290 m2/g, suspended in the molten raw material. Catalyst concn., 0.75% (recalcd. for pure Ni, 0.15%), was crucial to yield stearin with I no. < 1 in 60 min at 180°C and 2 MPa from raws of I no. = 60. At 160, 170, 180, and 190°C, the 1st-order reaction rate consts. were 0.225, 0.245, 0.269, and 0.312 min-1 as detd. over the first 15 min; the 160–200°C activation energy was 38.3 kJ/ mole.
13
Content available remote Kinetyka uwodornienia benzenu na katalizatorze niklowym w warunkach przemysłowych
PL
Wyznaczono zależności kinetyczne w reakcji uwodornienia benzenu na katalizatorze KUB-3 w laboratoryjnym reaktorze Temkina w zakresie parametrów procesu przemysłowego. Zaproponowano równanie kinetyczne opisujące szybkość reakcji w funkcji temperatury, stopnia przemiany, ciśnienia i stosunku wodór/benzen.
EN
A method was developed for differential kinetic studies run in a Temkin reactor under conditions of initial reaction rate over a 45% NiO/AI2O3-CaO (KUB-3) catalyst, φ 5 mm, 7 grains kept in a thermostated channel and sepd. by glass spheres. The reactor was operated in a differential regime, conversion ≤ 10%, with the bed working under nearly isothermic conditions. Studies on the effects of temp. (t = 150-250°C at 0.3 MPa), deg. of C6H6 → C6H12 conversion (x = 5-80%) overall pressure (p = 0.2-0.6 MPa at 200°C), and H2/C6H6 mole ratio (s = 0.5-7 at 200°C, 0.3 MPa) showed the hydrogenation rate (rB) to follow Authors' original empirical eqn., rB = A · f(t) · f(x) · f(p) · f(s) · (1-Kx/Kp), where A = const (at 200°C, 0.3 MPa, s = 3, x = 5%); f(t), f(x), f(p) and f(s) - polynomials of the resp. variables, and the term in parentheses describes the distance from equil.
EN
The effect of supports (Al2O3, Al2O3-TiO2, SiO2, SiO2-TiO2 and TiO2) on hydrogenation activity of nickel and platinum catalysts has been studied. The Ni and Pt content of the samples was fixed at 5 wt.% and 0.5 wt.% respectively The deposition of TiO2 on surface of both Al2O3 and SiO2 supports increases hydrogenation activity of the catalysts. A comparison of activity of the Ni/Al2O3-TiO2 and the Ni/SiO2-TiO2 catalysts proved that the SiO2-TiO2 supports are better both for use of nickel and platinum catalysts. Pt/SiO2-TiO2 catalysts exhibited high catalytic activity in the hydrogenation of toluene at lower temperature range.
EN
The activity of commercial catalyst which contained 50% of ZSM-5 zeolite (in nickel form) and silica was compared with the activities of zeolite (50% of Ni, H-ZSM-5) laboratory catalysts which included aluminium oxide and nickel oxide (8 wt.%). Determinations were carried out with n-hexane (T=275 to 400 C, H2 : CH=7 : LHSV=1h-1) and a mixture of paraffin hydrocarbons (p=5.0 and 7.0 MPa, H2:CH=500 Nm3/m3, LHSV=2h-1). The experimental result show that the commercial dewaxing catalyst displayed lower hydrocracking activity than laboratory catalysts. Determinations of catalytic activity using hydrotreated light diesel oil (p=3.5 MPa, LHSV=3h-1, H2:CH=500 Nm3/m3) have revealed that the activity of the catalyst obtained on the aluminium oxide can be modified by decreasing ion exchange level in the zeolite. Hydrocracking activity of catalyst was found to decrease considerably when zeolite content was reduced from 50 to 30 wt.%.
EN
Alumina-zeolite (50 wt.% Ni,H-ZSM-5) suppored nickel catalysts (8 wt.% NiO) were investigationed for hydrocracking of hydrotreated light vacum gas oil. The influence of the methods zeolite/metal incorporation on the activity, acidity and pore distributions were examined. The experiments evidenced that, the catalyst prepared via mixing peptisates (both obtained separately) of zeolite and aluminium hydroxide displayed the highest activity and stability. For this catalyst nickel was incorporated during aluminium hydroxide peptization. When nickel was incorporated with aluminosilicate hydrogel as a peptization agent the catalyst was more rapidly deactivated.
PL
Przedstawiono wyniki badań wpływu metod preparatyki (sposób wprowadzenia zeolitu oraz niklu) na własności, aktywność oraz stabilność katalizatorów zawierających 8% mas NiO. Przedmiotem badań były katalizatory zawierające 50% mas zeolitu Ni, H-ZSM-5. Stwierdzono, że największą aktywnością i stabilnością w procesie katalitycznego odparafinowania lekkiego oleju próżniowego charakteryzuje się katalizator, w preparatyce którego zastosowano metodę polegającą na łączeniu osobno przygotowanych peptyzatów zeolitu i wodorotlenku glinowego. Nikiel wprowadzono na eapie peptyzacji wodorotlenku glinowego. Aktywność katalizatorów ulega obniżeniu przy zastosowaniu podczas preparatyki hydrożelu glinokrzemianowego.
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