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1.
Selective catalytic reduction of NO x (SCR-NO x) with decane, and for comparison with propane and propene over Cu-ZSM-5 zeolite (Cu/Al 0.49, Si/Al 13.2) was investigated under presence and absence of water vapor. Decane behaves in SCR-NO x like propene, i.e. the Cu-zeolite activity increased under increasing concentration of water vapor, as demonstrated by a shift of the NO x–N 2 conversion to lower temperatures, in contrast to propane, where the NO x–N 2 conversion is highly suppressed. In situ FTIR spectra of sorbed intermediates revealed similar spectral features for C 10H 22– and C 3H 6–SCR-NO x, where –CH x, R–NO 2, –NO 3−, Cu +–CO, –CN, –NCO and –NH species were found. On contrary, with propane –CH x, R–NO 2, NO 3−, Cu +–CO represented prevailing species. A comparison of the in situ FTIR spectra (T–O–T and intermediate vibrations) recorded at pulses of propene and propane, moreover, under presence and absence of water vapor in the reaction mixture, revealed that the Cu 2+–Cu + redox cycle operates with the C 3H 6–SCR-NO x reactions in both presence/absence of water vapor, while with C 3H 8–SCR-NO x, the redox cycle is suppressed by water vapor. It is concluded that decane cracks to low-chain olefins and paraffins, the former ones, more reactive, preferably take part in SCR-NO x. It is concluded that formation of olefinic compounds at C 10H 22–SCR-NO x is decisive for the high activity in the presence of water vapor, while water molecules block propane activation. The increase in NO x–N 2 conversion due to water vapor in C 10H 22–SCR-NO x should be connected with the increased reactivity of intermediates. These are suggested to pass from R–NO x → –CN → –NCO → NH 3; the latter reacts with another activated NO x molecule to molecular nitrogen. The positive effect of water vapor on the NO x–N 2 conversion is attributed to increased hydrolysis of –NCO intermediates. 相似文献
2.
A rotary kiln reactor was evaluated for thermal recovery of oil from Utah oil sands. A series of continuous-flow pyrolysis experiments was conducted. Process variables investigated included temperature (748–848 K), solids retention time (10–27 min) and sweep gas flow rate (1.27–2.83 m s3 h −1). The results indicated that the pyrolysis temperature and the solids retention time were the two most important variables affecting the liquid and gas yields. The liquid yield (C 5+]) decreased and the gas yield (C 1–C 4) increased with increasing temperature. The liquid yield increased with decreasing solids retention time, while the gas yield decreased. No significant effect of the sweep gas flow rate on the product distribution and yields was observed. The quality of the bitumen-derived liquids was significantly better than that of the bitumen. A preliminary process kinetics model which conforms to the observed trends was proposed. 相似文献
3.
A single-event microkinetic model (SEMK) is applied to model initial coking rates during the catalytic cracking of (cyclo)alkane/1-octene mixtures at 693–753 K and (cyclo)alkane and 1-octene inlet partial pressures of 26.6 and 4.8 kPa on a REUSY equilibrium catalyst. Three types of irreversible alkylations involving both gas phase and surface coke precursors, viz., alkylation of phenyl substituted carbenium ions with C 3–C 5 alkenes, alkylation of the nucleus of monoaromatics with C 3–C 5 alkylcarbenium ions, and alkylation of C 8–C 10 alkylcarbenium ions with C 3–C 5 alkenes, have been considered as rate-determining steps in coke formation. The bulky alkylated species formed out of these alkylations are considered as coke. The activation energies for these alkylations obtained via non-isothermal regression are independent of the feedstock within the parameters confidence limits reflecting the fundamental character of the SEMK. The negative effect of temperature on the experimentally observed coking rates is qualitatively described and is explained in terms of an overcompensation of the increase of the rate coefficient by a lower surface coke precursor concentration. 相似文献
4.
The catalytic conversion of a methane and ethylene mixture to gasoline range hydrocarbons has been studied over W/HZSM-5 catalyst. The effect of process variables, such as temperature, percentage of volume of ethylene in the methane stream and catalyst loading on the distribution of hydrocarbons was studied. The reaction was conducted in a fixed-bed quartz-micro reactor in the temperature range of 300–500 °C using percentage of volume of ethylene in methane stream between 25 and 75% and catalyst loading of 0.2–0.4 g. The catalyst showed good catalytic performance yielding hydrocarbons consisting of gaseous products along with gasoline range liquid products. The mixed feed stream can be converted to higher hydrocarbons containing a high-liquid gasoline product selectivity (>42%). Non-aromatics C 5–C 10 hydrocarbons selectivity in the range of 12–53% was observed at the operating conditions studied. Design of experiment was employed to determine the optimum conditions for maximum liquid hydrocarbon products. The distribution of the gasoline range hydrocarbons (C 5–C 10 non-aromatics and aromatics hydrocarbons) was also determined for the optimum conditions. 相似文献
5.
The hydrogenation of CO over an Rh vanadate (RhVO 4) catalyst supported on SiO 2 (RhVO 4/SiO 2) has been investigated after H 2 reduction at 500°C, and the results are compared with those of vanadia-promoted (V 2O 5–Rh/SiO 2) and unpromoted Rh/SiO 2 catalysts. The mean size of Rh particles, which were dispersed by the decomposition of RhVO 4 after the H 2 reduction, was smaller (41 Å) than those (91–101 Å) of V 2O 5–Rh/SiO 2 and Rh/SiO 2 catalysts. The RhVO 4/SiO 2 catalyst showed higher activity and selectivity to C 2 oxygenates than the unpromoted Rh/SiO 2 catalyst after the H 2 pretreatment. The CO conversion of the RhVO 4/SiO 2 catalyst was much higher than that of V 2O 5–Rh/SiO 2 catalyst, and the yield of C 2 oxygenates increased. We also found that the RhVO 4/SiO 2 catalyst can be regenerated by calcination or O 2 treatment at high temperature after the reaction. 相似文献
6.
Effects of minerals on yields of C 3-C 8 volatiles from rapid pyrolysis of a Pittsburgh Seam bituminous coal were investigated. Whole, demineralized, and mineral-treated samples of pulverized coal were heated in 101 kPa He or 6.99 MPaH 2 at 1000 K s −1 to temperatures of up to 1300 K. Yields of C 3, C 4–C 6, and C 6–C 8 hydrocarbon gases were determined as a function of time-temperature history. Calcium minerals decrease yields of all three fractions in pyrolysis under He atmosphere but have little effect on hydropyrolysis. Kaolinite reduces yields in pyrolysis, but increases them in hydropyrolysis. Other minerals, notably FeSO 4, have varying effects on product yields depending on run conditions. 相似文献
7.
Crystallization of diamond was studied in the CO 2–C, CO 2–H 2O–C, H 2O–C, and CH 4–H 2–C systems at 5.7 GPa and 1200–1420°C. Thermodynamic calculations show generation of CO 2, CO 2–H 2O, H 2O and CH 4–H 2 fluids in experiments with graphite and silver oxalate (Ag 2C 2O 4), oxalic acid dihydrate (H 2C 2O 4·2H 2O), water (H 2O), and anthracene (C 14H 10), respectively. Diamond nucleation and growth has been found in the CO 2–C, CO 2–H 2O–C, and H 2O–C systems at 1300–1420°C. At a temperature as low as 1200°C for 136 h there was spontaneous crystallization of diamond in the CO 2–H 2O–C system. For the CH 4–H 2–C system, at 1300–1420°C no diamond synthesis has been established, only insignificant growth on seeds was observed. Diamond octahedra form from the C–O–H fluids at all temperature ranges under investigation. Diamond formation from the fluids at 5.7 GPa and 1200–1420°C was accompanied with the active recrystallization of metastable graphite. 相似文献
8.
The adsorption properties of a commercial Pd/Al 2O 3 catalyst were studied and compared with those of the Al 2O 3 support of the same specific surface area. Inverse gas chromatography (IGC) was used to determine the adsorption isotherms of five n-alkanes (C 8–C 12) in the 200–230 °C temperature range. Moreover, heats of adsorption, solubility coefficients and free energy of adsorption, are also reported. Interaction parameters of polar molecules with the stationary phase have also been determined and compared with those for the n-alkanes. Experiments with both the reduced and oxidized catalyst have been carried out by IGC and the results compared with those obtained by temperature programmed reduction (TPR) experiments. 相似文献
9.
The reaction condition for high yield of methanol in a gaseous reaction between methane and oxygen in the presence of NO at atmospheric pressure was explored. Methane partial oxidation without NO (CH 4–O 2) gave only 1% conversion of methane at 966 K. The addition of NO led to a remarkable increase in methane conversion and to high selectivity to C 1-oxygenates. The conversion of methane attained 10% at 808 K in the presence of NO (0.5%) where the selectivities to methanol and formaldehyde were 22.1 and 24.1%, respectively. Nitromethane and carbon oxides were also observed in the product gas. The amount of nitromethane was almost equal and/or near to that of initial NO. The carbon monoxide produced was several times higher than carbon dioxide. Influences of NO concentration, ratio of methane to oxygen, water vapor, and dilution with helium gas on product distribution were measured. Low concentration of NO (0.35–0.55%) was favorable for methanol formation. High selectivity to methanol was obtained at low value of the ratio of methane to oxygen (2.0–3.0) or low concentration of dilution gas (<16%). The NO 2 added promoted methane partial oxidation and selectivity to methanol. Therefore, it was assured that NO x promoted the formation of CH 3√ and CH 3O√ in the gas phase reaction for CH 4–O 2–NO. 相似文献
10.
Future regulations for the limitation of sulfur and aromatics in fuels driven by the European Auto Oil Program (AOP II) stimulate the need for an alternative utilization of the resulting surplus of pyrolysis gasoline (pygas). The conversion of heavy pyrolysis gasoline into valuable steam cracker feedstock with a maximum yield of C 2–C 4 n-alkanes is achieved via the ARINO ® two-step process, jointly developed by Linde, VEBA Oil and Süd-Chemie. The first step involves a hydrogenation of aromatics to naphthenes followed by the subsequent ring opening and cracking in the second step. Süd-Chemie developed a new commercial cracking catalyst for the second step of the ARINO® process with the aim to maximize the yield of C2–C4 n-alkanes at low formation of methane and aromatics. The ring opening and cracking reaction of naphthenes was studied in a bench scale tubular reactor over extruded H-ZSM-5 based zeolite catalysts. In a series of screening tests using a commercial, hydrogenated and desulphurized heavy pyrolysis gasoline, the influence of the preparation parameters such as zeolite acidity, palladium content as well as the type of binder were investigated. Furthermore, the influence of the process conditions space velocity and temperature was studied. High yields of C2–C4 n-alkanes at low formation of undesired methane and aromatics were achieved over an alumina bound zeolite with medium Brønsted acidity loaded with palladium. The reduction of the space velocity resulted in an increase in the C2–C4 n-alkane yield and lower formation of aromatics, but a simultaneous increase in the methane make. Raising the temperature from 280 to 370 °C significantly increased the catalyst activity. 相似文献
11.
Mesoporous molecular sieves (MCM-41 and SBA-15) with different pore diameters have been studied as supports of high loading of Co catalysts, and the performances in FT synthesis have been examined with a fixed bed stainless steel reactor at 2.0 MPa for the purpose of efficient production of C 10–C 20 fraction as the main component of diesel fuel. The method of exchanging template ions in uncalcined MCM-41 with Co 2+ ions is effective for holding 10–20% Co within the mesopores while keeping the structure regularity of MCM-41 to some extent, compared with the conventional impregnation method using calcined MCM-41. At 523 K, CO conversion and selectivity to C 10–C 20 hydrocarbons are both higher at larger loading of 20% Co for the exchanged catalysts with pore diameters of 2.7–2.9 nm. When four kinds of 20% Co/SBA-15 with the diameters of 3.5–13 nm, prepared by the impregnation method using an ethanol solution of Co acetate, are used in FT synthesis at 523 K, the catalyst with the diameter of 8.3 nm shows the largest CO conversion, which is higher than those over MCM-41 supported Co catalysts. At a lower temperature of 503 K, however, the acetate-derived Co is almost inactive. In contrast, the use of Co nitrate alone or an equimolar mixture of the acetate and nitrate as Co precursor drastically enhances the reaction rate and consequently provides high space–time yield (260–270 g C/kg cat h) of C 10–C 20 hydrocarbons. The X-ray diffraction and temperature-programmed reduction measurements show that the dependency of the catalytic performance of 20% Co/SBA-15 on its precursor originates probably from the differences in not only the reducibility of the calcined catalyst but also the dispersion of metallic Co. Catalyst characterization after FT synthesis strongly suggests the high stability of the most effective Co/SBA-15 in the dispersion and reducibility of the oxide species and in the mesoporous structure. 相似文献
12.
The reaction mechanism and the rate-determining step (RDS) of the isomerisation of n-alkanes (C 4–C 6) over partially reduced MoO 3 catalysts were studied through the effects of the addition of an alkene isomerisation catalyst (i.e. CoAlPO-11). When an acidic CoAlPO-11 sample was mechanically mixed with the MoO 3, a decrease of the induction period and an increase of the steady-state conversion of n-butane to isobutane were observed. These data support previous assumptions that a bifunctional mechanism occurred over the partially reduced MoO 3 (a complex nanoscale mixture of oxide-based phases) during n-butane isomerisation and that the RDS was the skeletal isomerisation of the linear butene intermediates. The only promotional effect of CoAlPO-11 on the activity of partially reduced MoO 3 for C 5–C 6 alkane hydroisomerisation was a reduction of the induction period, as the RDS at steady-state conditions appeared to be dehydrogenation of the alkane in this case. However, lower yields of branched isomers were observed in this case, the reason of which is yet unclear. 相似文献
13.
Effect of additives, In 2O 3, SnO 2, CoO, CuO and Ag, on the catalytic performance of Ga 2O 3–Al 2O 3 prepared by sol–gel method for the selective reduction of NO with propene in the presence of oxygen was studied. As for the reaction in the absence of H 2O, CoO, CuO and Ag showed good additive effect. When H 2O was added to the reaction gas, the activity of CoO-, CuO- and Ag-doped Ga 2O 3–Al 2O 3 was depressed considerably, while an intensifying effect of H 2O was observed for In 2O 3- and SnO 2-doped Ga 2O 3–Al 2O 3. Of several metal oxide additives, In 2O 3-doped Ga 2O 3–Al 2O 3 showed the highest activity for NO reduction by propene in the presence of H 2O. Kinetic studies on NO reduction over In 2O 3–Ga 2O 3–Al 2O 3 revealed that the rate-determining step in the absence of H 2O is the reaction of NO 2 formed on Ga 2O 3–Al 2O 3 with C 3H 6-derived species, whereas that in the presence of H 2O is the formation of C 3H 6-derived species. We presumed the reason for the promotional effect of H 2O as follows: the rate for the formation of C 3H 6-derived species in the presence of H 2O is sufficiently fast compared with that for the reaction of NO 2 with C 3H 6-derived species in the absence of H 2O. Although the retarding effect of SO 2 on the activity was observed for all of the catalysts, SnO 2–Ga 2O 3–Al 2O 3 showed still relatively high activity in the lower temperature region. 相似文献
14.
Characteristics of MnO y–ZrO 2 and Pt–ZrO 2–Al 2O 3 as reversible sorbents of NO x were investigated under dynamic changes in atmosphere. These sorbents can be used reversibly with a change of C 3H 8 concentration in the reaction gases. Catalytic reduction of NO occurred in the presence of propane, which was more pronounced on Pt–ZrO 2–Al 2O 3 than on MnO y-ZrO 2 due to high activity of Pt surface for this reaction on MnO y in MnO y–ZrO 2. The sorption was observed as soon as the atmosphere changed from a reducing to an oxidizing one. This implies that a high equilibrium partial pressure of O 2 is necessary for NO uptake since the sorbed NO−3 species becomes stable. The beginning of NO x desorption atmospheres was somewhat dependent on the amount of stored NO x. The presence of propane in the gas phase strongly affected the characteristic sorption and desorption properties of MnO y–ZrO 2 and Pt–ZrO 2–Al 2O 3. The sorption and desorption properties are different for MnO y–ZrO 2 and Pt–ZrO 2–Al 2O 3, since the noble metal or metal oxide possesses unique activity for the NO reaction with C 3H 8 and the amount of oxygen available for oxidative sorption of NO. 相似文献
15.
The selectivity for higher hydrocarbons (C 11–C 17) has been studied in the Fischer-Tropsch synthesis using fresh and used fused iron catalysts under different reaction conditions. On increasing the temperature higher hydrocarbon products were formed in the C 11–C 17 range. The deactivated fused iron catalyst is less active but selective to heavier hydrocarbon chain molecules. The product distribution is shifted towards heavier hydrocarbons due to the effects of the pore volume, presence of potassium and site densities at the surface. 相似文献
16.
Reaction mechanism of the reduction of nitrogen monoxide by methane in an oxygen excess atmosphere (NO–CH 4–O 2 reaction) catalyzed by Pd/H-ZSM-5 has been studied at 623–703 K in the absence of water vapor, in comparison with the mechanism for Co-ZSM-5. Kinetic isotope effect for the N 2 formation in NO–CH 4–O 2 vs. NO–CD 4–O 2 reactions was 1.65 at 673 K and decreased with a decrease in the reaction temperature. In addition, H–D isotopic exchange took place significantly in NO–(CH 4+CD 4)–O 2 reaction. These results are in marked contrast with the case of Co-ZSM-5, for which the C–H dissociation of methane is the only rate-determining step, and show that the C–H dissociation is slow but not the only rate-determining step in the case of Pd/H-ZSM-5. A reaction scheme was proposed, in which the relative rates of the three steps ((i)–(iii) below) vary depending on the reaction conditions. Further, in contrast to Co-ZSM-5, NO x–CH 4–O 2 reaction was much slower than CH 4–O 2 reaction for Pd/H-ZSM-5; the presence of NO x retards the reaction of CH 4 over the latter catalyst, while it accelerates the reaction over the former. It is suggested that CH 4 is activated directly by the Pd atoms in the case of Pd/H-ZSM-5, but by NO 2 strongly adsorbed on Co ion for Co-ZSM-5. The reaction order of the NO–CH 4–O 2 reaction with respect to NO pressure was consistent with this mechanism; 1.05 for Pd/H-ZSM-5 and 0.11 for Co-ZSM-5. 相似文献
17.
Low density polyethylene was dissolved into toluene and converted at 500 °C over three different commercial FCC catalysts in a laboratory Riser Simulator reactor. Short reaction-times up to 12 s were used. All the catalysts had qualitatively similar behaviors. The specific contribution of the polymer to the product slate of FCC was centered in hydrocarbons in the range of gasoline, with high aromatic content and highly olefinic C 3–C 4 gases. Saturated C 4–C 5 products were mainly isoparaffins. The additional coke formed by the polymer would make coke yields to increase moderately in relation to the standard operation. These facts confirmed that this recycling option, which is based on a proven technology, represents an interesting alternative to solve a major environmental problem. 相似文献
18.
The oxidation state of palladium on SiO 2–Al 2O 3 used for propane combustion was examined by XPS and XRD, and the correlation of the catalytic activity with the oxidation state of palladium was systematically studied. The propane conversion over 5 wt% Pd/SiO 2–Al 2O 3 was measured in the range 1.0≤ S≤7.2 ( S is defined as [O 2]/5[C 3H 8] based on stoichiometric ratio). The propane conversion strongly depended on the S value and reached the maximum at S=5.5. The oxidation state of palladium also changed with the S value; palladium particles were more oxidized under the reaction mixture of higher S value. On the sample used for the reaction at S=5.5, both of metallic palladium and palladium oxide were found. It is concluded that partially oxidized palladium which has optimum ratio of metallic palladium to palladium oxide shows the highest catalytic activity in propane combustion. 相似文献
19.
Ammonium polyacrylate (NH 4PA) was introduced into powdered mixtures consisting of anatase-structured TiO 2 nanoparticles and silicon alkoxide precursors at the sol level, and the rheological behavior of the mixtures was examined under various solid loadings (φ=0.05–0.13 in volumetric ratios), shear rates (
s −1) and NH 4PA concentrations. The alkoxide precursors were mixtures of tetraethyl orthosilicate (TEOS, Si(OC 2H 5) 4), ethyl alcohol (C 2H 5OH), H 2O and HCl in a constant [H 2O]/[TEOS] ratio of 11. The nanoparticle–sol mixtures generally exhibited a pseudoplastic flow behavior over the shear-rate regime examined. The NH 4PA appeared to serve as an effective surfactant which facilitates the suspension flow by reducing the flow resistance at low NH 4PA concentrations. At φ=0.10, a viscosity reduction ca. 85% was found at
s −1 when the NH 4PA concentration was held at 2.5 wt.% of the solids. As the NH 4PA exceeded a critical level, e.g., [NH 4PA]≥3.0 wt.%, the NH 4PA acted as a catalyst which quickly turned the TiO 2–silica sol mixtures (φ=0.10) into a gelled structure, resulted in a pronounced increase of mixture viscosity. The maximum solids concentration ( φm) of the mixtures was experimentally determined from a derivative of relative viscosity, i.e., (1−η r−1/2)– φ dependence. The estimated φm increased from 0.127 to 0.165 when NH 4PA of 0.5 wt.% was introduced into the TiO 2–silica sol mixtures. 相似文献
20.
Monolithic structures made of cordierite, γ-Al 2O 3 and steel have been prepared as catalysts and tested for Fischer–Tropsch activity. The monoliths made of cordierite and steel were washcoated with a 20 wt.% Co–1 wt.% Re/γ-Al 2O 3 Fischer–Tropsch catalyst whereas the γ-Al 2O 3 monoliths were made by direct impregnation with an aqueous solution of the Co and Re salts resulting in a loading of 12 wt.% Co and 0.5 wt.% Re. The activity and selectivity of the different monoliths were compared with the corresponding powder catalysts. Higher washcoat loadings resulted in decreased C5+ selectivity and olefin/paraffin ratios due to increased transport limitations. The impregnated γ-Al2O3 monoliths also showed similar C5+ selectivities as powder catalysts of small particle size (38–53 μm). Lower activities were observed with the steel monoliths probably due to experimental problems. 相似文献
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