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1.
Catalytic wet air oxidation (CWAO) of aqueous solution of phenol was carried out with pure oxygen at 160 °C in a stirred batch reactor on platinum supported oxide catalysts (Pt/CeO2c calcined at 650 and 800 °C and Pt/CexZr1 − xO2 with x = 0.90, 0.75 and 0.50). The catalysts were characterized before (BET, FT-IR spectroscopy, hydrogen chemisorptions, oxygen storage capacity (OSC)) and after reaction (TPO, elementary analysis, GC–MS and DTA–TGA). The results demonstrate a poisoning of the catalysts during CWAO reaction due to the formation of different forms of carbon deposit on the materials: carbonates and polymeric carbon species. This poisoning phenomenon is limited by the introduction of 50% of zirconium into ceria lattice for the catalysts presenting the lowest surface area. Polymeric deposits play a major role in the catalyst deactivation.  相似文献   

2.
The steam reforming of phenol towards H2 production was studied in the 650–800 °C range over a natural pre-calcined (air, 850 °C) calcite material. The effects of reaction temperature, water, hydrogen, and carbon dioxide feed concentrations, and gas hourly space velocity (GHSV, h−1) were investigated. The increase of reaction temperature in the 650–800 °C range and water feed concentration in the 40–50 vol% range were found to be beneficial for catalyst activity and H2-yield. A similar result was also obtained in the case of decreasing the GHSV from 85,000 to 30,000 h−1. The effect of concentration of carbon dioxide and hydrogen in the phenol/water feed stream was found to significantly decrease the rate of phenol steam reforming reaction. The latter was probed to be related to the reduction in the rate of water dissociation as evidenced by the significant decrease in the concentration of adsorbed bicarbonate and OH species on the surface of CaO according to in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS)-CO2 adsorption experiments in the presence of water and hydrogen in the feed stream. Details of the CO2 adsorption on the CaO surface at different reaction temperatures and gas atmospheres using in situ DRIFTS and transient isothermal adsorption experiments with mass spectrometry were obtained. Bridged, bicarbonate and unidentate carbonate species were formed under CO2/H2O/He gas mixtures at 600 °C with the latter being the most populated. A substantial decrease in the surface concentration of bicarbonate and OH species was observed when the CaO surface was exposed to CO2/H2O/H2/He gas mixtures at 600 °C, result that probes for the inhibiting effect of H2 on the phenol steam reforming activity. Phenol steam reforming reaction followed by isothermal oxygen titration allowed the measurement of accumulated “carbonaceous” species formed during phenol steam reforming as a function of reaction temperature and short time on stream. An increase in the amount of “carbonaceous” species with reaction time (650–800 °C range) was evidenced, in particular at 800 °C (4.7 vs. 6.7 mg C/g solid after 5 and 20 min on stream, respectively).  相似文献   

3.
ZnO doped with Bi2O3 and Sb2O3 (ZBS), is the basic system for ceramic varistors. Phase formation during sintering of ZBS was measured in situ, using 1 mm thick samples and synchrotron X-rays. Sintering shrinkage was measured in different atmospheres by an optical method. Thermodynamic calculations were performed to explain phase formation, composition, stability of additive oxides and influence of the oxygen fugacity on sintering. Sb2O4, pyrochlore, trirutile and spinel were formed at temperatures of 500–800 °C. The oxidation of antimony was controlled by the oxygen partial pressure and affected both, phase formation and sintering kinetics, in the ZBS system.  相似文献   

4.
A number of catalysts based on Al2O3 loaded with doped Ce-Zr mixed oxides and different active components (Cu, Cu-Ni, Ru, Pt, etc.) were synthesized via standard wet impregnation method using the robotic workstation. Ethanol (EtOH) was taken as a model compound of bio-oil and steam reforming of ethanol (ESR)—as a model reaction. Activity screening experiments performed at 600–700 °C in 0.5 vol.% C2H5OH + 2.5 vol.% H2O + 97 vol.% He mixture revealed that the most effective catalyst composition is Ru/Ce0.4Zr0.4Sm0.2/Al2O3. Catalytic activity investigations at high reagent concentrations (10 vol.% C2H5OH + 40 vol.% H2O + 50 vol.% N2) at 650–800 °C confirmed this fact, revealing also that at high temperatures the activity of Cu-Ni catalysts is comparable with that of Ru-containing catalyst.  相似文献   

5.
An adapted sol–gel method allowed synthesizing SmCoO3 and PrCoO3 oxides with high specific surface (ca. 28 m2 g−1) and a relatively clean perovskite phase at 600 °C, a temperature much lower than the one required in ceramic methods. The perovskites were investigated as catalysts for the oxidation of ethane in the temperature range 300–400 °C. Both catalysts were very active: ethane was activated already at 300 °C, i.e., 100 °C below the temperatures previously reported for perovskites. The main product was CO2 on both catalysts, but on PrCoO3 oxidehydrogenation (ODH) to ethylene was observed already at 300 °C, with the low selectivity. Even so, this was quite unusual for simple perovskites, and for such a low temperature. TPR data showed that praseodymium decreases the reducibility of Co3+ in the perovskite, what could explain the observed ODH, and suggest it proceeds via a Mars–van Krevelen mechanism. Kinetic study showed a similar apparent activation energy for both catalysts (ca. 80 kJ/mol), but a difference in the nature of the participating oxygen species: while on PrCoO3 both adsorbed and lattice species contribute to the reaction, on SmCoO3 contribution of adsorbed species is practically negligible, due to its very high oxygen lability. The results show that these simple perovskites may be promising catalysts for ethane oxidation at relatively low temperatures.  相似文献   

6.
A series of samples of La–Cr–O– perovskites were designed as catalysts for diesel soot combustion. They were prepared by using co-precipitation method, at ambient temperature using ammonia followed by a hydrothermal treatment (T = 200 °C, P = 20 atm, t = 24 h). All the chromium-containing precursors were then calcined at high temperature to develop the oxide catalyst. Two phase composition 86%LaCrO3–(14%) La2CrO6 or 94%LaCrO3–6%La2O3 were formed depending on the atmosphere of calcination (oxygen or hydrogen respectively) used. Their respective BET surface areas were 1.1 and 6.5 m2 g−1. Highly crystalline, pure phase of LaCrO3 and La2CrO6 powders were also prepared, with BET area of 4 and 3 m2 g−1, respectively. The crystalline structure and properties of all samples were characterised by X-ray diffraction (XRD), using Rietveld refinement, and temperature-programmed reduction (TPR) techniques. O2-TPD measurements performed on all samples showed the presence of suprafacial, weakly chemisorbed oxygen only for LaCrO3, which contributes actively to soot combustion. TPR study performed on all catalysts showed that while pure LaCrO3 and La2O3 samples did not reduce, the biphasic catalysts showed the presence of oxygen depletion peaks characteristic of lattice oxygen mobility in the samples at ca. 665 °C. Catalytic combustion of diesel soot was studied over all catalysts. The results showed that pure LaCrO3 exhibited significant catalytic activity which was sensitively affected by the modifier La2CrO6 or La2O3.  相似文献   

7.
Supported nickel catalysts of composition Ni/Y2O3–ZrO2 were synthesized in one step by the polymerization method and compared with a nickel catalyst prepared by wet impregnation. Stronger interactions were observed in the formed catalysts between NiO species and the oxygen vacancies of the Y2O3–ZrO2 in the catalysts made by polymerization, and these were attributed to less agglomeration of the NiO during the synthesis of the catalysts in one step. The dry reforming of ethanol was catalyzed with a maximum CO2 conversion of 61% on the 5NiYZ catalyst at 800 °C, representing a better response than for the catalyst of the same composition prepared by wet impregnation.  相似文献   

8.
The reduction of NO to N2/N2O in the presence of excess O2 has been successfully achieved at 70 °C using an electrochemical cell of the type, 0.1% NO, 0–10% O2, Pt | NAFION | Pt, H2O. An H+-conducting solid polymer electrolyte (SPE) plays a key role in evolving hydrogen on the Pt cathode, where the catalytic NO–H2 takes place. It was revealed that the competitive H2–O2 reaction is suppressed because the Pt surface was covered with stable nitrate (NO3) species, which blocks oxygen adsorption hereon. The inhibition of H2–O2 reaction becomes most efficient at 100 °C in agreement with the optimal operation temperature range of SPE. The reduction efficiency of NO in an excess O2 could be improved by packing 1 wt% Pt/ZSM-5 catalyst in the cathode room. The combination between the SPE cell and Pt catalysts can broadly be applied to novel low-temperature deNOx processes in a strongly oxidizing atmosphere.  相似文献   

9.
Mo–V–X (X = Nb, Sb and/or Te) mixed oxides have been prepared by hydrothermal synthesis and heat-treated in N2 at 450 °C or 600 °C for 2 h. The calcination temperature and the presence or absence of Nb determines the nature of crystalline phases in the catalyst. Nb-containing catalysts heat-treated at 450 °C are mostly amorphous solids, while Nb-free catalysts heat-treated at 450 °C and samples treated at 600 °C clearly contain crystalline phases. TPR-H2 experiments show higher H2-consumption on catalysts with amorphous phases. Catalytic results in the oxidative dehydrogenation of ethane indicate that the selective production of the olefin is strongly related to the development of the orthorhombic Te2M20O57 or (SbO)2M20O56 (M = Mo, V, Nb) phase (the so-called M1 phase), which is mainly formed at 600 °C. This active and selective crystalline phase is characterized to show moderate reducibility and active centers enough for the selective oxidative activation of ethane with the minimum quantity possible of active centers for ethylene activation. In this sense, the best yield to ethylene has been achieved on a Mo–V–Te–Nb mixed oxide.  相似文献   

10.
The purpose of this study was the synthesis of lithium disilicate glass-ceramics in the system SiO2–Al2O3–K2O–Li2O. A total of 8 compositions from three series were prepared. The starting glass compositions 1 and 2 were selected in the leucite–lithium disilicate system with leucite/lithium disilicate weight ratio of 50/50 and 25/75, respectively. Then, production of lithium disilicate glass-ceramics was attempted via solid-state reaction between Li2SiO3 (which was the main crystalline phase in compositions 1 and 2) and SiO2. In the second series of compositions, silica was added to fine glass powders of the compositions 1 and 2 (in weight ratio of 20/100 and 30/100) resulting in the modified compositions 1–20, 1–30, 2–20, and 2–30. In the third series of compositions, excess of silica, in the amount of 30 wt.% and 20 wt.% with respect to the parent compositions 1 and 2, was introduced directly into the glass batch. Specimens, sintered at 800 °C, 850 °C and 900 °C, were tested for density (Archimedes’ method), Vickers hardness (HV), flexural strength (3-point bending tests), and chemical durability. Field emission scanning electron microscopy and X-ray diffraction were employed for crystalline phase analysis of the glass-ceramics. Lithium disilicate precipitated as dominant crystalline phase in the crystallized modified compositions containing colloidal silica as well as in the glass-ceramics 3 and 4 after sintering at 850 °C and 900 °C. Self-glazed effect was observed in the glass-ceramics with compositions 3 and 4, whose 3-point bending strength and microhardness values were 165.3 (25.6) MPa and 201.4 (14.0) MPa, 5.27 (0.48) GPa and 5.34 (0.40) GPa, respectively.  相似文献   

11.
Oxygen storage capacity (OSC) of CeO2–ZrO2 solid solution, CexZr(1−x)O4, is one of the most contributing factors to control the performance of an automotive catalyst. To improve the OSC, heat treatments were employed on a nanoscaled composite of Al2O3 and CeZrO4 (ACZ). Reductive treatments from 700 to 1000 °C significantly improved the complete oxygen storage capacity (OSC-c) of ACZ. In particular, the OSC-c measured at 300 °C reached the theoretical maximum with a sufficient specific surface area (SSA) (35 m2/g) after reductive treatment at 1000 °C. The introduced Al2O3 facilitated the regular rearrangement of Ce and Zr ions in CeZrO4 as well as helped in maintaining the sufficient SSA. Reductive treatments also enhanced the oxygen release rate (OSC-r); however, the OSC-r variation against the evaluation temperature and the reduction temperature differed from that of OSC-c. OSC-r measured below 200 °C reached its maximum against the reduction temperature at 800 °C, while those evaluated at 300 °C increased with the reduction temperature in the same manner as OSC-c.  相似文献   

12.
A natural Maghnia clay was pillared by Al13 and impregnated by 3–10 wt.% Me (Me = Rh, Ni, Pd, Ce) to be used as catalysts in the reforming of methane with carbon dioxide to synthesis gas. The structural and textural properties of materials calcined at 450 °C were determined by several techniques (XRD, FT-IR, 27Al magic angle spinning (MAS) NMR, X-ray photoelectron spectroscopy (XPS), BET, thermogravimetric analysis (TGA)–DSC, H2-temperature programmed reduction (TPR) and NH3-TPR). Although impurities are present in the Al-pillared layered clay (PILC) support, most properties are close to those of pure Al-pillared Na-montmorillonite. Impregnation and calcination leads to the plugging of most micropores by clusters or microparticles of oxides. The NMR resonances of AlVI and AlIV specie are not modified after impregnation, and AlVI/AlIV ratio only varies on loading when compared to Al-PILC. Catalytic experiments show that the most active catalyst is 3% Rh/Al-PILC on which 88 mol.% of methane is converted at 650 °C with a minimum amount of carbon deposit. The conversions decrease along the 3% Rh ≈ 10% Ni > 3% Pd > 3% Ni > 3% Ce series. The H2/CO ratio amounts to 1.1 with Rh and to 0.85 with Pd which are metallic at the temperature of reaction, but it has a lower value with Ni and Ce due to the RWGS reaction known to proceed in the presence of oxides.  相似文献   

13.
N2O decomposition was investigated over a series of K-promoted Co-Al catalysts. The activity tests showed that doping with K greatly enhanced the catalytic activity of the Co-Al catalyst, and the enhancement was critically dependent on the amount of K and the calcination temperature. When the catalyst had a K/Co atomic ratio of 0.04 and was calcined at 700–800 °C, a full N2O conversion could be reached at a reaction temperature of 300 °C. Moreover, even under the simultaneous presence of 4% O2 and 2.6% water vapor, such high-temperature treated K/Co-Al catalyst exhibited high reactivity and stability, with the N2O conversion remaining at a constant value of 92% over 40 h run at 360 °C. In contrast, non-doped Co-Al catalyst showed a severe activity loss under such reaction conditions. A combination of characterization techniques was employed to reveal the promoting role of K and the effect of calcination temperature. The results suggest that doping with K increases the electron density of Co and weakens the Co–O bond, thus promoting the activation of N2O on the Co sites and facilitating the desorption of oxygen from the catalyst surface. High-temperature calcinations made the desorption of O2 proceed more readily.  相似文献   

14.
The reactivity of adsorbed NO (including NO2) and NH3 in the presence of 4.0% oxygen in He was examined over a pitch-based ACF calcined at 800°C. Regeneration at 30°C by 4% O2 in He without NH3 was found to be optimum for the recovery of the initial activity with complete removal of NO within 3 h, with minimum leaks of adsorbed NO and NH3. A higher temperature of 40°C for regeneration increased the liberation of adsorbed NO, and NH3 over ACF was rather slow at a lower temperature of 25°C, slow regeneration being achieved. Oxygen appears necessary to regenerate the ACF through enhancing the reaction of adsorbed NO and NH3 for the initial activity, which was ascribed to the catalytic activity for NO–NH3 and adsorption of both NO and NH3. NH3 in the gas phase appears to inhibit the regeneration reaction of adsorbed species, by using the leaking amount during the regeneration.  相似文献   

15.
Several nickel-based catalysts (Ni/Al2O3, Ni/MgO, Ni/CeO2, Ni/ZSM-5, Ni-Al, Ni-Mg-Al and Ni/CeO2/Al2O3) have been prepared and investigated for their suitability for the production of hydrogen from the two-stage pyrolysis–gasification of polypropylene. Experiments were conducted at a pyrolysis temperature of 500 °C and gasification temperature was kept constant at 800 °C with a catalyst/polypropylene ratio of 0.5. Fresh and reacted catalysts were characterized using a variety of methods, including, thermogravimetric analysis, scanning electron microscopy with energy dispersive X-ray spectrometry and transmission electron microscopy. The results showed that Ni/Al2O3 was deactivated by two types of carbons (monoatomic carbons and filamentous carbons) with a total coke deposition of 11.2 wt.% after reaction, although it showed to be an effective catalyst for the production of hydrogen with a production of 26.7 wt.% of the theoretical yield of hydrogen from that available in the polypropylene. The Ni/MgO catalyst showed low catalytic activity for H2 production, which might be due to the formation of monoatomic carbons on the surface of the catalyst, blocking the access of gaseous products to the catalyst. Ni-Al (1:2) and Ni-Mg-Al (1:1:2) catalysts prepared by co-precipitation showed good catalytic abilities in terms of both H2 production and prevention of coke formation. The ZSM-5 zeolite with higher surface area was also shown to be a good support for the nickel-based catalyst, since, the Ni/ZSM-5 catalyst showed a high rate of hydrogen production (44.3 wt.% of theoretical) from the pyrolysis–gasification of polypropylene.  相似文献   

16.
A number of nano-gold catalysts were prepared by depositing gold on different metal oxides (viz. Fe2O3, Al2O3, Co3O4, MnO2, CeO2, MgO, Ga2O3 and TiO2), using the homogeneous deposition precipitation (HDP) technique. The catalysts were evaluated for their performance in the combustion of methane (1 mol% in air) at different temperatures (300–600 °C) for a GHSV of 51,000 h−1. The supported nano-gold catalysts have been characterized for their gold loading (by ICP) and gold particle size (by TEM/HRTEM or XRD peak broadening). Among these nano-gold catalysts, the Au/Fe2O3 (Au loading = 6.1% and Au particle size = 8.5 nm) showed excellent performance. For this catalyst, temperature required for half the methane combustion was 387 °C, which is lower than that required for Pd(1%)/Al2O3 (400 °C) and Pt(1%)/Al2O3 (500 °C) under identical conditions. A detailed investigation on the influence of space velocity (GHSV = 10,000–100,000 cm3 g−1 h−1) at different temperatures (200–600 °C) on the oxidative destruction of methane over the Au/Fe2O3 catalyst has also been carried out. The Au/Fe2O3 catalyst prepared by the HDP method showed much higher methane combustion activity than that prepared by the conventional deposition precipitation (DP) method. The XPS analysis showed the presence of Au in the different oxidation states (Au0, Au1+ and Au3+) in the catalyst.  相似文献   

17.
The rate of Fischer–Tropsch synthesis over an industrial well-characterized Co–Ru/γ-Al2O3 catalyst was studied in a laboratory well mixed, continuous flow, slurry reactor under the conditions relevant to industrial operations as follows: temperature of 200–240 °C, pressure of 20–35 bar, H2/CO feed ratio of 1.0–2.5, gas hourly space velocity of 500–1500 N cm3 gcat− 1 h− 1 and conversions of 10–84% of carbon monoxide and 13–89% of hydrogen. The ranges of partial pressures of CO and H2 have been chosen as 5–15 and 10–25 bar respectively. Five kinetic models are considered: one empirical power law model and four variations of the Langmuir–Hinshelwood–Hougen–Watson representation. All models considered incorporate a strong inhibition due to CO adsorption. The data of this study are fitted fairly well by a simple LHHW form − RH2 + CO = apH20.988pCO0.508 / (1 + bpCO0.508)2 in comparison to fits of the same data by several other representative LHHW rate forms proposed in other works. The apparent activation energy was 94–103 kJ/mol. Kinetic parameters are determined using the genetic algorithm approach (GA), followed by the Levenberg–Marquardt (LM) method to make refined optimization, and are validated by means of statistical analysis. Also, the performance of the catalyst for Fischer–Tropsch synthesis and the hydrocarbon product distributions were investigated under different reaction conditions.  相似文献   

18.
Silica-supported copper prepared by a sol–gel method can selectively catalyze methanol steam reforming to hydrogen and carbon dioxide at 250 °C. The catalytic activity increases with the copper content up to 40 wt.%. The selectivity to carbon monoxide with the catalysts containing 20–40 wt.% of copper is significantly lower than that with a commercial Cu/ZnO/Al2O3 catalyst. Copper particles are highly dispersed in the catalyst whose Cu content is 20 wt.% or less. After the reaction at 250 °C the particles are present as Cu2O with the mean crystallite size less than 4 nm. In the catalyst with the Cu content of 30–50 wt.%, the fine Cu2O particles coexist with large metallic Cu particles whose mean crystallite size is 30–40 nm after the reaction. The large metallic particles are supposed to contribute to the reaction as well as the fine Cu2O particles although the surface area is estimated to be significantly smaller than that of the latter.  相似文献   

19.
Low sintering temperature ZnNb2O6 microwave ceramics were prepared by doping with mixed oxides of V2O5–Bi2O3 and V2O5–Bi2O3–CuO. The effects of additives on the microstructure and dielectric properties of the ceramics were investigated. The results show that doping with V2O5–Bi2O3 can reduce the sintering temperature of ZnNb2O6 from 1150 °C to 1000 °C due to the formation of V2O5 and Bi2O3 based eutectic phases. The combined influence of V2O5 and Bi2O3 resulted in rod-like grains. Co-doping CuO with 1 wt.% V2O5–1 wt.% Bi2O3 further lowered the sintering temperature to 880 °C, because eutectic phases could be formed between the CuO, V2O5 and Bi2O3. A second phase of (Cu2Zn)Nb2O8 also forms when the content of CuO is greater than 2.5 wt.%. A pure ZnNb2O6 phase can be obtained when the amount of CuO was 1.0–2.5 wt.%. The Q × f values of ZnNb2O6 ceramics doped with V2O5–Bi2O3–CuO were all higher than 25,000 GHz. The dielectric constants were 22.8–23.8 at microwave frequencies. In addition, theτf values decreased towards negative as the content of CuO increased. The ceramic with composition of ZnNb2O6 + 1 wt.%V2O5 + 1 wt.% Bi2O3 + 2.5 wt.% CuO sintered at 880 °C exhibited the optimum microwave dielectric properties, is 23.4, Q × f is 46,975 GHz, and τf is −44.89 ppm/°C, which makes it a promising material for low-temperature co-fired ceramics (LTCCs).  相似文献   

20.
The objective of the present study was to select the optimal catalyst and operating conditions for the manufacture of C9-alcohol, using C9-aldehyde and hydrogen, in a trickle bed reactor. When CaO, Ce2O3 or MgO was added as a promoter to the Ni/kieselguhr catalyst, the BET and Ni surface areas were increased. In the reaction for the manufacture of C9-alcohol, using C9-aldehyde and hydrogen in a batch reactor, a Ni–MgO/kieselguhr catalyst showed the highest activity. In addition, the catalyst using Na2CO3 as a precipitant showed the highest activity. According to the result of an experiment to find the optimal reaction conditions for C9-alcohol synthesis, using C9-aldehyde and hydrogen in a trickle bed reactor loaded with Ni–MgO/kieselguhr catalyst, the highest yield of C9-alcohol was 91.5 wt% at 130 °C, 400 psi and WHSV = 3. The C9-aldehyde hydrogenation performance of the Ni–MgO/kieselguhr catalyst was similar to that of a Cu/ZnO/Al2O3 catalyst, but superior to that of Cu–Ni–Cr–Na/Al2O3 and Ni–Mo/Al2O3 catalysts. In a long-term catalysis test, the Ni–MgO/kieselguhr catalyst showed higher stability than the Cu/ZnO/Al2O3 catalyst.  相似文献   

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