首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
The conversion of monochloropropanes and dichloropropanes over acid catalysts has been investigated in the presence of oxygen. In the temperature range of 450–550 K, dehydrochlorination of monochloropropanes to propene and HCl occurs selectively over silica–alumina, while significant formation of chlorinated by-products is observed over ZSM5 zeolite catalyst even at higher temperatures. Dichloropropanes conversion over silica–alumina catalyst gives rise mainly to chloropropenes in the temperature range 500–700 K. COx are predominant products only at the highest reaction temperatures (just above 700 K). Water vapor in the feed only slightly affects conversions and selectivities. Deactivation processes occur upon dichloropropane conversion, mainly due to coke deposition.

The conversion of highly chlorinated compounds, such as trichloroethylene (TCE) has been tested over silica–alumina and over HY zeolite in the presence of water vapor in the so-called “steam reforming” conditions (HVOC:water=1:2). With diluted feed (1200 ppm) on HY, reaction occurs above 800 K and formation of chlorinated by-products is minimized, COx being the main reaction products. At higher HVOC concentrations conversion is obtained at even lower temperature (600 K), but no more negligible by-products formation has been detected. In our conditions zeolite catalyst is more effective in TCE total conversion than silica–alumina.  相似文献   


2.
R. Yan  D. Gauthier  G. Flamant  J. M. Badie 《Fuel》1999,78(15):1817-1829
The behaviours of ten minor coal elements (Al, Ca, Fe, K, Mg, Mn, Na, P, Si and Ti) during coal combustion in the temperature range 400–2000 K, under both oxidising and reducing conditions, have been studied in detail by a thermodynamic equilibrium analysis.

The partitioning of these elements is calculated both in single minor element–coal–chlorine systems and in minor elements co-existing systems. Their vaporisation tendency is found in the order: (Si, Al)<(Fe, Ti)<(Ca, Mn)<(K, Na, P, Mg). Si, Ti, Al and P are present mostly as oxides and K and Na as chlorides, whatever the combustion conditions. Al, Ca, Fe, K, Mn and Na sulphates are dominant at low temperatures under oxidising conditions, whereas under reducing conditions most of them are sulphides and/or chlorides. Moreover, the interactions between these elements affect their major speciation: some species containing two elements among those studied are dominant in the minor elements co-existing systems. The affinities of minor coal elements to sulphur have been studied versus both temperature (400 or 800 K) and sulphur content (0.0062–6.20 wt.% in the coal), in order to find out their influence on the flue gas desulfurization. Two coal samples with different ash contents were considered, and it was found that the ash composition affects greatly the minor elements partitioning.  相似文献   


3.
The partial oxidation of ethanol was investigated over Ru and Pd catalysts supported onto yttria over a wide range of temperatures (473–1073 K). The product distributions obtained over these catalytic systems were correlated with diffuse reflectance infrared spectroscopy analyses (DRIFTS). Results showed that reaction route depended strongly on the type of metal. The decomposition of ethoxy species to CH4 and CO or oxidation to CO2 was promoted by Pd, and the acetaldehyde desorption was predominant over Ru in the low temperature region. Furthermore, the acetate and carbonate formation prevailed over Pd, which explained the lower acetaldehyde selectivity. The presence of CH4 and CO2 at high temperature is assigned to the decomposition of acetate species via carbonates over Pd-based catalysts. Ru was more suitable system for H2 production than Pd by achieving a selectivity of about 59%.  相似文献   

4.
The activity of dimethyl ether (DME) hydrolysis was investigated over a series of solid acid and non-acid catalysts, zeolite Y [Si/Al = 2.5 and 15: denoted Y(Si/Al)], zeolite ZSM-5 [Si/Al = 15, 25, 40, and 140: denoted Z(Si/Al)], silica, zirconia, γ-alumina, and BASF K3-110 (commercial Cu/ZnO/Al2O3 catalyst). Dimethyl ether hydrolysis was carried out in an isothermal packed-bed reactor at ambient pressure.

Acid catalyzed dimethyl ether hydrolysis is equilibrium limited. All solid acid catalysts, with the exception of ZrO2, attained equilibrium-limited conversions in the temperature range of interest (125–400 °C). Z(15), Z(25), and Z(40) reached equilibrium conversions at 200 °C, while Z(140), Y(15), and Y(2.5) reached equilibrium at 275 °C. γ-Alumina, the most active non-zeolite solid acid, attained equilibrium at 350 °C. Silica and BASF K3-110 were both ineffective in converting dimethyl ether to methanol. The observed activity trend for DME hydrolysis to methanol as a function of Si–Al ratio and catalyst type was:

  相似文献   

5.
Perovskite type La1 − xSrxMnO3 (x = 0–0.5) oxides were prepared by the amorphous citrate process, characterised by X-ray diffraction, oxygen desorption, temperature-programmed reduction, infrared and X-ray photoelectron spectroscopic techniques, and tested for methane combustion within the 473–1073 K temperature range. Since catalyst activity was found to depend strongly on BET areas and to a lesser extent, on the degree of substitution (x), intrinsic activities were computed for La1 − xSrxMnO3 catalyst series. Among the compositions investigated, the degree of substitution x = 0.2 showed the highest intrinsic activity within the temperatures explored. Characterisation techniques made possible to correlate catalytic performance with the structural characteristics of the oxides. The stability of Mn4+ is probably the most important parameter, but excess of oxygen and atomic surface composition should also be taken into account.  相似文献   

6.
The objective of this research is to asses the impact of the addition of H2O, SO2, and both in the SCR of NO at low temperatures over sulphated vanadia on carbon-coated monoliths. The sulphated catalyst keeps a 100% conversion and total selectivity to N2 in the low temperature range, i.e. 473–500 K, when either H2O or SO2 is added to the gas feed. However, a decline of steady state conversion and selectivity occurs when both H2O and SO2 are added simultaneously because H2O speeds up the deposition of ammonium sulphate salts. This decrease of catalyst performance is reversed when the reaction is carried out under dry conditions at temperatures higher than 473 K but not at lower temperature (453 K). Thus, the catalyst has demonstrated to be a good candidate for the SCR of NO at low temperatures even in stack gases containing traces of undesired components.  相似文献   

7.
The nature of the adsorbed species on Cu-ZSM-5 (Cu-Z), Cu-Mordenite (Cu-M), and Cu-Y-zeolite (Cu-Y) was investigated by means of temperature programmed desorption (TPD). When dinitrogen monoxide (N2O) came into contact with Cu-zeolites above 573 K, the decomposition of N2O occurred accompanied by the formation of adsorbed oxygen species and adsorbed nitrogen oxide species. In the TPD runs, three O2 desorption peaks appeared at temperatures of 623, 673, and 753 K and were named -, β-, and γ-peaks, respectively. The O2 desorption at the - and γ-peaks became quickly saturated after contacting N2O at 598 K, while the amount of O2 desorbed at the β-peak increased with time, not reaching a constant level until 120 min of exposure. The activity for the decomposition of N2O decreased with the accumulation of β-oxygen over the catalyst. The rate of N2O decomposition depended upon the nature and amount of the copper zeolite catalysts available, as determined by the formation of - and/or β-oxygen.  相似文献   

8.
The oxidation of benzene to phenol has been successfully carried out in air over Cu-ZSM-5 at moderate temperatures. Several parameters such as Cu loading, calcination temperature and co-exchanged metal ions influence the nature of the catalyst. At low Cu loadings, the catalyst is more selective to phenol while at high Cu loadings CO2 is the major product. In situ H2-TPR XAFS studies reveal that at low Cu loadings, Cu exists as isolated pentacoordinated ions, with 4 equatorial oxygens at 1.94 Å and a more distant axial oxygen at 2.34 Å. At higher loadings, monomeric as well as dimeric Cu species exist, with a Cu–Cu distance of 2.92 Å. This suggests that the isolated Cu sites are the active sites responsible for phenol formation. When the catalyst was calcined at 450 °C, the activity peaked in the first hour and then slowly deactivated, but when the calcination temperature was increased to 850 °C, the activity slowly increased until it reached a plateau. Analysis of the XANES region during in situ H2-TPR shows that at lower calcination temperatures two reduction peaks are present, corresponding to Cu2+ → Cu+ and Cu+ → Cu0. At high calcination temperatures, only a small fraction of the Cu undergoes the two-step reduction and most of the Cu remains in the +2 state. Slow deactivation of the catalyst calcined at 450 °C is due to migration of the Cu ions to inaccessible sites in the zeolite; at high calcination temperatures the Cu is tightly bound to the framework and is unable to migrate. EXAFS analysis of the sample calcined at 850 °C reveals two Cu–Si(Al) scattering paths at 2.83 Å. Doping the catalyst with other metals, in particular Ag and Pd, further improves the activity and selectivity of the reaction. The addition of water to the reaction increases the selectivity of the reaction by displacing the product from the active site.  相似文献   

9.
G. Piehl  T. Liese  W. Grünert   《Catalysis Today》1999,54(4):333-406
ZSM-5 zeolite was loaded with vanadyl ions (VO2+) by treatment of Na–ZSM-5 with aqueous VOSO4 solution at pH 1.5–2. The catalytic material was tested for the selective catalytic reduction of NO with ammonia at temperatures between 473 and 823 K and normal pressure using a feed of 1000 ppm NO, 1000 (or 1100) ppm NH3 and 2% O2 in He. The catalyst proved to be highly active, providing, e.g. initial NO conversions of >90% at 620 l g−1 h−1 (≈400 000 h−1) and 723 K, and selective, providing nitrogen yields equal to NO conversion at equimolar feed in a wide temperature range and only minor N2O formation at NH3 excess. Admixture of SO2 (200 ppm) resulted in an upward shift of the useful temperature range, but did not affect the catalytic behaviour at temperatures ≥623 K. No SO2 conversion was noted at T ≤ 723 K and 450 l g−1 h−1. The poisoning effect of water (up to 4.5 vol%) was weak at temperatures between 623 and 773 K. VO-ZSM-5 catalysts are gradually deactivated already under dry conditions, probably by oxidation of the vanadyl ions into pentavalent V species. This deactivation is considerably accelerated in the presence of water.  相似文献   

10.
Kaolin was dealuminated until the SiO2/Al2O3 molar ratio (R) was raised to values of 2.4 and 2.9 mole SiO2/mole Al2O3 by chemical reaction with: (i) aqueous HCl; or reaction at high temperature with (ii) NaHSO4 or (iii) H2SO4. Dealuminated samples were introduced into a sodium–potassium hydroxide solution under reaction conditions for the gel formation step in zeolite X synthesis using kaolin plus additional Si.

Samples dealuminated with HCl showed Si reaction yields (XSi) in the range of 0.10–0.20, slightly higher than the values obtained with calcined kaolin or calcined kaolin plus quartz. On the other hand, Al reaction yields (XAl) were in the range of 0.02–0.03, similar to the values obtained for kaolin plus additional Si. Samples dealuminated with NaHSO4 showed XSi values in the range of 0.50–0.60, above those obtained for kaolin plus additional Si. Conversely, XAl values were in the range of 0.04–0.05, resembling the values obtained for kaolin plus additional Si. In contrast, samples dealuminated with H2SO4 showed XSi values in the range of 0.40–0.50, above the values obtained for kaolin plus additional Si. At the same time, XAl reached values resembling those obtained with samples dealuminated with NaHSO4 for long reaction times, or kaolin plus additional Si.

The values of XSi can be explained in terms of total pore volume and fractal surface dimension deduced through N2 isotherms at 77 K.  相似文献   


11.
An extensive series of 30 Cu exchanged zeolites and Cu impregnated silicas and aluminas have been tested in their capacities to stabilize the bis(μ-oxo)dicopper core. This core shows a remarkably activity towards methane, as it selectively hydroxylates methane into methanol at the low temperature of 125 °C. UV–vis spectroscopy is an easy approach to detect the presence of this bis(μ-oxo)dicopper core since it is characterized by an intense charge transfer band at 22 700 cm−1. In this way it was found that after calcination, only the Cu exchanged zeolites ZSM-5 and MOR are capable of stabilizing this core. In addition, an optimum in the Si/Al ratio and in the calcination temperature were observed, indicating that this core requires a rather specific coordination environment. For ZSM-5, the optimal Si/Al ratio for bis(μ-oxo) dicopper core formation is between 12 and 30 and the amount of this core increases with increasing copper loading above Cu/Al = 0.2. Calcination in O2 should be done at temperatures higher than 280 °C and lower than 700 °C. After reaction with methane at low temperature (150 °C), it was found that only Cu-ZSM-5 and Cu-MOR yielded methanol, whereas all the other Cu based materials yielded almost no methanol. At higher temperatures (200 °C) however, Cu-FER and Cu-BEA showed comparable methanol yields as Cu-ZSM-5 and also the methanol yield of Cu-MOR increased at this higher reaction temperature, indicating that a second not yet identified Cu-oxygen species is activated in the FER, BEA and MOR zeolites at higher temperatures.  相似文献   

12.
The influences of calcination temperatures and additives for 10 wt.% Cu/γ-Al2O3 catalysts on the surface properties and reactivity for NO reduction by C3H6 in the presence of excess oxygen were investigated. The results of XRD and XPS show that the 10 wt.% Cu/γ-Al2O3 catalysts calcined below 973 K possess highly dispersed surface and bulk CuO phases. The 10 wt.% Cu/γ-Al2O3 and 10 wt.% Mn–10 wt.% Cu/γ-Al2O3 catalysts calcined at 1073 K possess a CuAl2O4 phase with a spinel-type structure. In addition, the 10 wt.% La–10 wt.% Cu/γ-Al2O3 catalyst calcined at 1073 K possesses a bulk CuO phase. The result of NO reduction by C3H6 shows that the CuAl2O4 is a more active phase than the highly dispersed and bulk CuO phase. However, the 10 wt.% Mn–10 wt.% Cu/γ-Al2O3 catalyst calcined at 1073 K possesses significantly lower reactivity for NO reduction than the 10 wt.% Cu/γ-Al2O3 catalyst calcined at 1073 K, although these catalysts possess the same CuAl2O4 phase. The low reactivity for NO reduction for 10 wt.% Mn–10 wt.% Cu/γ-Al2O3 catalyst calcined at 1073 K is attributed to the formation of less active CuAl2O4 phase with high aggregation and preferential promotion of C3H6 combustion to COx by MnO2. The engine dynamometer test for NO reduction shows that the C3H6 is a more effective reducing agent for NO reduction than the C2H5OH. The maximum reactivity for NO reduction by C3H6 is reached when the NO/C3H6 ratio is one.  相似文献   

13.
Uniform nano-sized beta-silicon carbide (β-SiC) powder was synthesized from the reaction of silicon (Si) and carbon black (C). Mixed Si and C-black powder were pressed into pellets and the influence of four parameters, temperature (1250, 1300 and 1350 °C), heating rate (20 and 50 °C/min), soaking time (1 and 3 h) and atmosphere (vacuum and argon), were tested. It was found that higher temperatures, higher heating rates and longer soaking times in a vacuum system lead to lower free Si content in the SiC powder created. Temperature was the parameter with the greatest influence on the Si content of the SiC powder. This study also found that the Si–C reaction occurs through gas–solid (SiO–C) and solid–solid (Si–C) reactions that occur simultaneously.  相似文献   

14.
ZSM-5 zeolite films were grown on Si substrates by a two-step hydrothermal synthesis consisting of in situ seeding and secondary crystal growth. The films were 8–13 μm thick and partly oriented with the c-axis perpendicular to the substrate surface. After ion exchange with sodium ions, one film was applied as solid electrolyte in a potentiometric hydrocarbon gas sensor. A fast and reversible voltage response of the sensor to varying propane concentrations (100 ppm – 10%) was observed in O2/CO2/N2 gas mixtures at 723 K.  相似文献   

15.
Variation of the Si/Al ratio in nanosized zeolite Beta crystals   总被引:3,自引:0,他引:3  
Zeolite Beta nanocrystals were prepared from basic aluminosilicate precursor solutions upon hydrothermal treatment at 100 °C. The Si/Al ratio of the initial system was systematically changed from 25 to infinity in order to study the limits in the framework composition of BEA-type crystallites synthesized from clear basic solutions. Furthermore, the effect of the Si/Al ratio on the precursor species, ultimate crystal size, morphology and yield was investigated. The results revealed that the crystallization kinetics of nanosized Beta are dependent on the amount of Al in the precursor solutions, that is, the nucleation and growth processes are faster in Al-rich systems. The crystallization process of zeolite Beta with Si/Al ratios in the initial solutions of 14, 23 and 32 was accomplished within 72 h, whereas longer crystallization times, 140 and 264 h, were necessary to obtain crystalline products with Si/Al ratios of 42 and infinity, respectively. The intermediates and final products were investigated by complementary techniques such as XRD, HRTEM, DLS, IR, NMR spectroscopy and chemical analysis. Low temperature (77 K) CO adsorption infrared spectroscopy was used to study the Brønsted acidity of zeolite Beta samples with different Si/Al ratios. The properties of Beta nanocrystals important for the design of catalysts and selective separation materials are provided based on the results obtained from the detailed characterization.  相似文献   

16.
The kinetics of N2O decomposition to gaseous nitrogen and oxygen over HZSM-5 catalysts with low content of iron (<400 ppm) under transient and steady-state conditions was investigated in the temperature range of 250–380 °C. The catalysts were prepared from the HZSM-5 with Fe in the framework upon steaming at 550 °C followed by thermal activation in He at 1050 °C. The N2O decomposition began at 280 °C. The reaction kinetics was first order towards N2O during the transient period, and of zero order under steady-state conditions. The increase of the reaction rate with time (autocatalytic behaviour) was observed up to the steady state. This increase was assigned to the catalysis by adsorbed NO formed slowly on the zeolite surface from N2O. The formation of NO was confirmed by temperature-programmed desorption at temperatures >360 °C. The amount of surface NO during the transient increases with the reaction temperature, the reaction time, and the N2O concentration in the gas phase up to a maximum value. The maximum amount of surface NO was found to be independent on the temperature and N2O concentration in the gas phase. This leads to a first-order N2O decomposition during the transient period, and to a zero-order under steady state. A kinetic model is proposed for the autocatalytic reaction. The simulated concentration–time profiles were consistent with the experimental data under transient as well as under steady-state conditions giving a proof for the kinetic model suggested in this study.  相似文献   

17.
The influence of the nature of the Zn, Al and Pt precursors, and of the temperature of precipitation and aging have been studied in connection with the preparation of Zn/Al and Pt/Zn/Al layered double hydroxides (LDH) by the sol–gel method. Whatever the precursors the XRD analysis shows that LDH is formed at the expense of ZnO when the precipitation and aging temperatures decrease from 353 K to 273 K. Moreover, chemical composition and TG analysis suggest the presence of weak amounts of hydrozincite, hydrozincite-like and Al(OH)3 phases. When the precursors are Zn acetate-2-hydrate or Al acetylacetonate the amount of LDH reaches a maximum of 50 mol% at 273 K. At variance, about 90 mol% of LDH is obtained when using Zn acetylacetonate and Al isopropoxide as precursors, which are precipitated at 273 K. This proportion is slightly improved for the Pt-containing sample prepared under the same conditions. The specific surface areas of the different samples obtained after calcination at 723 K increase with their LDH content, reaching values of 110–120 m2 g−1. They make them particularly attractive for catalytic applications.  相似文献   

18.
H2/D2 exchange (473–583 K), 1,3-butadiene hydrogenation (418–513 K) and tetrahydrothiophen hydrodesulphurisation (428–557 K) have been studied over powdered Co9S8 (surface area, 7 m2 g−1) using D2 as an isotopic tracer. Hydrogen exchange proceeded as a first order process at a modest rate (k540 = 1.0 h−1 m−2) with an apparent activation energy of 67 kJ mol−1. Butadiene hydrogenation was diagnostic as to the surface state of Co9S8; samples showed either predominant 1:2-addition or 1:4-addition of hydrogen, interpreted as indicating the presence in the surface of single sites or pair/ensemble sites, respectively. Reactions at 473 K in the presence of D2 gave butenes containing 0–6 D-atoms: exchange patterns obtained from these D-distributions showed that a proportion of butadiene molecules underwent extensive dehydrogenation during the normal progress of hydrogenation. At 633 K this dehydrogenation activity was evident as self-hydrogenation which occurred in the absence of D2. Tetrahydrothiophen was desulphurised in the presence of D2 to thiophen (void of D), butadiene (containing 0–5 D-atoms) and 1-butene (containing mostly 0 and 4 D-atoms). Increase in temperature or in deuterium pressure favoured butene formation so that it became the dominant product (88%). Tetrahydrothiophen also underwent self-hydrodesulphurisation in the absence of D2. A mechanism is proposed, consistent with this D-tracer information, that accommodates dehydrogenation, desulphurisation and hydrogenation steps in the overall process. The activity of powdered Co9S8 exceeded that of powdered MoS2.  相似文献   

19.
The topological structure of IM-5 zeolite has remained a mystery for nearly 10 years. Stimulated by the recently structural solution of IM-5, we firstly report the computational study on the Al locations, acid sites and acid strength, which are important to understand the catalytic mechanism of IM-5. At the B3LYP/6-31+G(d,p) level, the 8T models were applied. The substitutions of Si by Al atom at 24 inequivalent tetrahedral crystallographic sites and the corresponding H proton localizations were examined by calculating the Al, H substitution energies, proton affinities, the atomic charges on proton and hydroxyl stretching vibrational frequencies. Based on the calculated results it was predicted that the most favorable sites for Al atom substitution in IM-5 were T4, T5, T14, T15 and T19 sites, whereas the least favorable sites were T1, T3, T8, T11, and T16 sites. There are about 40 preferable Al, H locations with relatively high acidity, including the nine strongest acid sites Al19H43 > Al14H18 > Al5H13 > Al4H8 > Al10H26, Al15H26, Al15H37, Al22H45 and Al24H47. The last five sites have equivalent proton affinity values. The numerous Al, H-sites with high acidity may be responsible for the high catalytic ability of IM-5. The calculated results should be helpful for understanding the chemistry of IM-5, the most complicated zeolite material known up to now.  相似文献   

20.
The influence of framework and extraframework composition of USY zeolite on the catalytic performance of bifunctional Pt/USY (1 wt.% Pt) catalysts for the coupled hydrogenation and ring opening of 1-methylnaphthalene (1-MN) has been studied on a continuous fixed bed high pressure reactor. All Pt/USY catalysts showed very high methylnaphthalene (MN) conversions under the reaction conditions studied (T=300–375 °C, P=4.0 MPa, WHSV=2 h−1, H2/1-MN=30 mol/mol). Product yields and selectivities were mainly determined by the zeolite composition (i.e. acidity). Selectivity to products with the same number of carbon atoms than the feed (C11) increased, at constant temperature, with decreasing the Brönsted acidity of the USY zeolite, that is, with decreasing the concentration of framework Al (FAL) and increasing extraframework Al (EFAL). Selectivity to high cetane ring opening products (ROP=C11-alkylbenzenes (C11AB) and C11-alkylcycloalkanes) within the C11 fraction was higher for the less acidic catalysts. A maximum yield of ROP of ca. 15 wt.% at a C11 yield of ca. 73 wt.% was obtained at 350 °C (P=4.0 MPa, WHSV=2 h−1, H2/1-MN=30 mol/mol) for a USY zeolite with an intermediate degree of dealumination (a0=24.33 Å) and containing all the EFAL (bulk Si/Al ratio of 2.6). For this catalyst, a slight increase in ROP yield (ca. 17 wt.%) at similar C11 yield (ca. 74 wt.%) was obtained by working at lower temperature (300 °C) and lower space velocity. Increasing the reaction pressure above 4.0 MPa had only a marginal influence on product yields and selectivities.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号