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EN
Biodiesel is currently preferred for consumption and has been widely used as a substitute for diesel. This study aimed to determine the effect of various methanol-to-oil ratios in the esterification process and also the effect of hydrotalcite catalyst weight on the transesterification product. The catalyst was characterized with SEM, XRD, FTIR, and TG-DTG-DTA. The esterification process was operated at various oil-to-methanol ratios, i.e., 1:12–1:36 and the transesterification was performed using several catalyst weights, 0.5%–2.5%. The results showed that the optimum conditions of esterification were at the 1:30 molar ratio of oil-to-methanol, which decreased the amount of acid number by 95.75%, while the optimum condition of transesterification was at 1.5% catalyst weight. The characteristics of biodiesel using 0.5–2% hydrotalcite catalyst (acid number, total glycerol, free glycerol, ester levels, viscosity, density, oxidation stability) have met the Indonesian biodiesel standard of SNI-04-7182-2012.
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.
PL
W pracy przedstawiono zależne od czasu zachowanie hydratacyjne mieszanin reaktywnych mikroproszków MgO i α-Al2O3 o stosunku molowym 2:1, 1:1 i 1:2 w związku z opracowaniem nowych hydraulicznych układów spoiw dla betonów ogniotrwałych złożonych ze spinelu in situ i korundu. Fazy Mg-Al-CO3 podobne do hydrotalkitu, które powstały w matrycach cementowych utwardzanych w odpowiednich warunkach przez 4 miesiące w temperaturze 50 °C, zostały poddane charakterystyce morfologicznej, chemicznej i strukturalnej za pomocą technik odpowiednio XRD, FT-IR i SEM. Rozkład termiczny produktów hydratacji matryc, zawierających magnez i glin o właściwościach wiążących, badano za pomocą połączonych technik DSC-TGA-EGA-MS. Główną różnicą pomiędzy uwodnionymi fazami utworzonymi w matrycach cementowych Mg-Al, otrzymanych przy różnych czasach utwardzania, jest stabilność termiczna wody międzywarstwowej i grup wodorotlenowych wewnątrz struktury minerałów warstwowego podwójnego wodorotlenku (LDH).
XX
This work investigates the time-dependent hydration behaviour of 2:1, 1:1 and 1:2 molar ratio mixtures of reactive MgO and α-Al2O3 micro-powders in relation to the development of new hydraulic binder systems for in situ spinel refractory corundum castables. Mg-Al-CO3 hydrotalcite-like phases, that formed in the cementitious matrices cured in the corresponding curing condition up to 4 months of age at a temperature of 50 °C, were subjected to morphological, chemical and structural characterization using XRD, FT-IR and SEM techniques, respectively. The thermal decomposition of the hydration products of Mg-Al cementitious matrices has been studied by simultaneous DSC-TGA-EGA-MS. The main difference between hydrated phases, that were formed in the Mg-Al cementitious matrices obtained at different curing times, is the thermal stability of interlayer water and hydroxyl groups within the structure of the layered double hydroxide (LDH) minerals.
EN
Saturated polyester resins were prepared by reaction of dimethylterephthalate with alkylene glycols in the presence of layered doublehydroxides (hydrotalcites, HT). The effect of HT composition (cation and aniontypes) on the rate and progress of transesterification was investigated. It was found that zinc-aluminum HT intercalated with anionic form of aminolauric acid[HT(ZnAl)ALA] efficiently catalyzes transesterification process, increasing therate of reaction or lowering its temperature when compared to the reaction with use of conventional organic tin catalyst. The polyester resin obtained in this way is transparent, which along with X-ray diffraction data indicates the delamination of clay layers and formation of nanocomposite. The limitation of using ALA-intercalated HT as an additive for polyesters used in coatings is coloration of the resin with an increase of the reaction temperature above 180°C. Colorless polyester was obtained using more thermally stable hydrotalciteintercalated with ethylenediaminetetraacetic acid, however, at the expense of significantly longer reaction time. Using HT(ZnAl)ALA catalyst a two-step synthesis of carboxyl polyester resin was performed and the obtained product was used as a component of powder coating formulation.
PL
Przeprowadzono syntezę nasyconych żywic poliestrowych w reakcji tereftalanu dimetylowego z glikolami alkilenowymi, w obecności warstwowego podwójnego wodorotlenku typu hydrotalkitu (HT). Analizowano wpływ składu HT na szybkość i wydajność transestryfikacji. Najlepsze wyniki (zwiększenie szybkości reakcji lub obniżenie średniej temperatury procesu w porównaniu z szybkością i temperaturą reakcji prowadzonej w obecności tradycyjnego katalizatora organocynowego) uzyskano z zastosowaniem hydrotalkitu interkalowanego kwasem aminolaurynowym (ALA). Otrzymane w taki sposób żywice były transparentne, co w połączeniu z zanikiem refleksów hydrotalkitu w widmie XRD produktu transestryfikacji może świadczyć o utworzeniu się delaminowanego nanokompozytu. Wykorzystanie HT interkalowanego ALA w żywicach poliestrowych stosowanych do powłok jest ograniczone ze względu na zabarwienie pojawiające się w temperaturze powyżej 180 °C. W reakcji prowadzonej z udziałem bardziej stabilnego termicznie hydrotalkitu modyfikowanego kwasem etylenodiaminotetraoctowym otrzymano bezbarwny poliester, jednak kosztem znacznego wydłużenia czasu reakcji. Katalizator HT(ZnAl)ALA zastosowano w dwustopniowej syntezie poliestru o łańcuchu zakończonym grupami karboksylowymi, który następnie użyto w charakterze składnika proszkowej kompozycji powłokowej.
5
Content available remote Oligomeryzacja glicerolu na hydrotalcytach Mg-Al modyfikowanych Zr
EN
Oligomerization of glycerol over Zr modified Mg-Al hydrotalcites
PL
Przedstawiono działania zmierzające do zaprojektowania i syntezy składowej kwasowej katalizatora hybrydowego służącego do otrzymywania DME z gazu syntezowego. W badaniach wykorzystano montmorillonit wydzielony ze skały bentonitowej z Milowic oraz handlowo dostępny montmorillonit K-10. Montmorillonit Na-mt wykorzystano także do otrzymania materiałów kompozytowych typu PILC (montmorillonit podpierany) i PCH (porowata heterostruktura). W pierwszym przypadku uzyskano wysokopowierzchniowy materiał mikroporowaty, w drugim wysokopowierzchniowy materiał mezoporowaty. Badano dwie formy kwasowe montmorillonitu: a) preparat H-mt uzyskany z formy sodowej w drodze wymiany jonowej w środowisku rozcieńczonego kwasu solnego, b) montmorillonit K-10, stanowiący produkt intensywnej aktywacji stężonym kwasem. Stwierdzono, że przeprowadzenie montmorillonitu w formę kwasową związane jest z modyfikacją jego struktury i tekstury. Stopień modyfikacji można kontrolować dobierając odpowiednio warunki obróbki kwasowej. Obie kwasowe formy montmorillonitu poddano impregnacji heteropolikwasem H3PW12O40. Właściwości strukturalne i teksturalne zależały od natury użytego nośnika (H-mt lub mt-K-10) oraz od sposobu przeprowadzenia impregnacji. Stwierdzono, że impregnacja HPW obniża wartość maksimum temperatury konwersji metanolu do DMT o ok. 90°C w porównaniu z układem niezawierającym HPW.
EN
Research part of this article deals with design and synthesis of the acidic component of hybrid catalyst for one step synthesis of DME from syngas. Montmorillonite fraction from Milowice bentonite and commercially available montmorillonite K-10 were used in the experiments. The composite materials e.g. PILC and PCH were obtained from Na-mt montmorillonite. The first is the high surface microporous material, the second is the high surface mezoporous material. Two acidic forms of montmorillonite were investigated: a) H-mt obtained from sodium form by ionic exchange in the presence of diluted hydrochloric acid, b) montmorillonite K-10, a product of intense activation with concentrated acid. It was found that the transformation of montomorillonite into acidic form is connected with the modification of its structure and texture. The degree of the modification can be controlled by selecting the appropriate conditions of acidic treatment. Both acidic forms of montmorillonite were impregnated by heteropolyacid H3PW12O40 (HPW). The structural and textural properties of montmorillonites impregnated with HPW depended on the nature of the support (H-mt or mt-K-10) and on the applied impregnation method (conventional or modified). The catalytic activity of the samples impregnated with HPW was higher than that of the starting material. It has been found that impregnation by HPW lowers the temperature of the maximum methanol conversion to DMT by about 90°C, in comparison with the system not comprising HPW.
8
Content available remote New magnetic Ni-Al hydrotalcite-like materials: synthesis and characterization
EN
Novel magnetic Ni-Al hydrotalcite with Ni/Al molar ratio of 3 was synthesized by the hydrothermal method and co-precipitation. The obtained material was characterized in detail by thermogravimetric analysis – differential scanning calorimetry, X-ray diffraction (XRD), transmission electron microscopy (TEM), and vibrating sample magnetometry (VSM). XRD analysis indicated that a more well-crystallized hydrotalcite-like phase and higher thermal stability were present in the hydrothermally treated product than in that obtained by the conventional co-precipitation method. Well-defined flat particles were observed by TEM, and the (200) lattice plane (d = 0.21 nm) could be clearly seen in the HRTEM image. Furthermore, VSM results showed that the obtained material exhibited paramagnetism.
EN
Aseries of Cu,Cr-layered double hydroxides of Cu/Cr ratio equal 2 has been synthesized by co-precipitation at a constant pH, using different preparative conditions. The investigated synthesis parameters included: ageing time, speed of reactants addition, temperature of co-precipitation and pH of synthesis. The dominant product of the synthesis was the nitrate form of Cu,Cr-LDH, containing ca. 10 mol% of carbonate. Modifications of experimental conditions affected chiefly the samples crystallinity. The most obvious effects were associated with changing of pH of the co-precipitation, the most acidic conditions providing a material of the best crystallinity. At the medium synthesis temperature (55°C), a slow addition of the reactants and a long ageing were favourable, but a significant shortening of the ageing time caused only minor deterioration of the sample crystallinity. The latter finding is of practical importance for an upscaling of the process.
EN
A layered organic-inorganic intercalate was prepared by the self-assembly technique using pamoate (PA) as an organic guest in the Zn-Al layered double hydroxide inorganic host (ZAPAN). Various concentrations of PA, ranging from 0.01 to 0.04 M, were used to prepare the intercalated compound with a constant 4:1 ratio of Zn:Al in the mother liquor. The concentration of PA of 0.02 M at pH 7 was found to give a well-ordered nanolayered organic-inorganic hybrid structure. As a result of successful intercalation of PA anion into the Zn-Al inorganic layered double hydroxide (LDH), the expansion of interlayer spacing to 18 A was observed in the PXRD diffractogram of the intercalated compound, compared to 9 A for the Zn-Al LDH with nitrate as the counter anion (ZANIL). FTIR study shows that the intercalated compound resembled the spectra of PA and ZANIL, thus indicating the presence of both functional groups in ZAPAN. It was also found that the BET surface area increased from 6 m2/g to 90 m2/g for ZANIL and ZAPAN, respectively. The pore texture of the resulting materials was also changed as the result of the intercalation and the expansion of the basal spacing together with pore formation between the crystallite during the formation of the resulting layered intercalated compound.
EN
Mg-Al layered double hydroxides containing carbonates and nitrates in theinterlayer gallery were used as parent materials for anion exchange. NO-3 and CO2-3 anions were exchanged with oxoanions containing vanadium, chromium, molybdenum and tungsten. Ion-exchange in basic solution led to introduction of V2O 4-7, CrO2-4, MoO2-4 and WO2-4 anions, while V10O286-, Cr2O2-7, Mo7O6-24 and W7O6-24 forms were intercalated in acidic solution. The intercalation was confirmed by X-ray diffraction and FTIR spectroscopy. Oxidative dehydrogenation of n-butane was carried out over hydrotalcite-derived catalysts. The catalysts obtained by thermal decompn. of V2O4-7-contg. Hydrotalcites appeared to be the most active ones in a prodn. of 1,3-butadiene. However, the highest yield of butenes was achieved over Mg-Al-Cr oxides catalyst in the low temp. range (Ł550C).
EN
The chemical composition of Mg-Al hydrotalcite was modified either by introduction of V3+ cations into the brucite-like sheets of double layered hydroxide or by exchange of the interlayer NO3- and CO32- anions with polyoxovanadate species. Pyrovanadate (V2O74-) and decavanadate (V10O286-) intercalated into Mg-Al hydrotalcite were obtained from the parent aqueous NH4VO3 solution by adjustment of pH to the value of 9.5 or 4.5, respectively. All the as-synthesized samples were characterized with respect to their structure by powder x-ray diffraction and IR spectroscopy. The calcined materials were used as catalysts in oxidative dehydrogenation of iso-butane performed in the excess of oxygen.
PL
Hydrotalkity wyjściowe Mg-Al (Mg/Al = 2) różniące się względnym udziałem anionów azotanowych i węglanowych zsyntezowano poprzez współstrącanie przy zachowaniu stałego pH. Metodę wymiany jonowej wykorzystano do wprowadzenia anionów poliwanadanowych (V2074- i V100286- _ do przestrzeni międzywarstwowych hydrotalkitów. Efektywność przeprowadzonej wymiany określono metodą proszkowej dyfrakcji rentgenowskiej (XRD) i spektroskopii w podczerwieni (FTIR). Interkalacja anionów pirowanadanowych przebiega łatwiej w przypadku użycia jako materiałów wyjściowych hydrotalkitów azotanowych. Rodzaj anionu międzywarstwowego (COl-, N031 nie odgrywa natomiast istotnej roli przy wprowadzaniu anionów dekawanadanowych.
EN
Parent hydrotalcites Mg-Al (Mg/Al = 2) varying in fraction of carbonate and nitrate anions incorporated into the interlayer space were synthesized by coprecipitation at constant pH. Ion-exchange method was used to intercalate polyoxovanadate anions (V2O74- and V10O286-) into hydrotalcite structure. Efficiency of ion-exchange was characterized by powder X-ray diffraction (XRD) and lR spectroscopy. Intercalation of pyrovanadate anions occurs easier for nitrate-containing hydrotalcites, while no difference in efficiency of the ion-exchange in the case of decavanadates is observed.
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