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1.
Effect of additives, In2O3, SnO2, CoO, CuO and Ag, on the catalytic performance of Ga2O3–Al2O3 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 H2O, CoO, CuO and Ag showed good additive effect. When H2O was added to the reaction gas, the activity of CoO-, CuO- and Ag-doped Ga2O3–Al2O3 was depressed considerably, while an intensifying effect of H2O was observed for In2O3- and SnO2-doped Ga2O3–Al2O3. Of several metal oxide additives, In2O3-doped Ga2O3–Al2O3 showed the highest activity for NO reduction by propene in the presence of H2O. Kinetic studies on NO reduction over In2O3–Ga2O3–Al2O3 revealed that the rate-determining step in the absence of H2O is the reaction of NO2 formed on Ga2O3–Al2O3 with C3H6-derived species, whereas that in the presence of H2O is the formation of C3H6-derived species. We presumed the reason for the promotional effect of H2O as follows: the rate for the formation of C3H6-derived species in the presence of H2O is sufficiently fast compared with that for the reaction of NO2 with C3H6-derived species in the absence of H2O. Although the retarding effect of SO2 on the activity was observed for all of the catalysts, SnO2–Ga2O3–Al2O3 showed still relatively high activity in the lower temperature region.  相似文献   

2.
An In2O3/Al2O3 catalyst shows high activity for the selective catalytic reduction of NO with propene in the presence of oxygen. The presence of SO2 in feed gas suppressed the catalytic activity dramatically at high temperatures; however it was enhanced in the low temperature range of 473–573 K. In TPD and FT-IR studies, the formation of sulfate species on the surface of the catalyst caused an inhibition of NOX adsorption sites, and the absorbance ability of NO was suppressed by the presence of SO2, and the amount of ad-NO3 species decreased obviously. This leads to a decrease of catalytic activity at higher temperatures. However, addition of SO2 enhanced the formation of carboxylate and formate species, which can explain the promotional effect of SO2 at low temperature, because active C3H6 (partially oxidized C3H6) is crucial at low temperature.  相似文献   

3.
A systematic reactivity study of N2O, NO, and NO2 on highly dispersed CuO phases over modified silica supports (SiO2–Al2O3, SiO2–TiO2, and SiO2–ZrO2) has been performed. Different reaction paths for the nitrogen oxide species abatement were studied: from direct decomposition (N2O) to selective reductions by hydrocarbons (N2O, NO, and NO2) and oxidation (NO to NO2). The oxygen concentration, temperature, and contact time, were varied within suitable ranges in order to investigate the activity and in particular the selectivity in the different reactions studied. The support deeply influenced the catalytic properties of the active copper phase. The most acidic supports, SiO2–Al2O3 and SiO2–ZrO2, led to a better activity and selectivity of CuO for the reactions of N2O, NO, and NO2 reductions and N2O decomposition than SiO2–TiO2. The catalytic results are discussed in terms of actual turnover frequencies starting from the knowledge of the copper dispersion values.  相似文献   

4.
Catalytic performance of Sn/Al2O3 catalysts prepared by impregnation (IM) and sol–gel (SG) method for selective catalytic reduction of NOx by propene under lean burn condition were investigated. The physical properties of catalyst were characterized by BET, XRD, XPS and TPD. The results showed that NO2 had higher reactivity than NO to nitrogen, the maximum NO conversion was 82% on the 5% Sn/Al2O3 (SG) catalyst, and the maximum NO2 conversion reached nearly 100% around 425 °C. Such a temperature of maximum NO conversion was in accordance with those of NOx desorption accompanied with O2 around 450 °C. The activity of NO reduction was enhanced remarkably by the presence of H2O and SO2 at low temperature, and the temperature window was also broadened in the presence of H2O and SO2, however the NOx desorption and NO conversion decreased sharply on the 300 ppm SO2 treated catalyst, the catalytic activity was inhibited by the presence of SO2 due to formation of sulfate species (SO42−) on the catalysts. The presence of oxygen played an essential role in NO reduction, and the activity of the 5% Sn/Al2O3 (SG) was not decreased in the presence of large oxygen.  相似文献   

5.
A novel TiO2/Al2O3/cordierite honeycomb-supported V2O5–MoO3–WO3 monolithic catalyst was studied for the selective reduction of NO with NH3. The effects of reaction temperature, space velocity, NH3/NO ratio and oxygen content on SCR activity were evaluated. Two other V2O5–MoO3–WO3 monolithic catalysts supported on Al2O3/cordierite honeycomb or TiO2/cordierite honeycomb support, two types of pellet catalysts supported on TiO2/Al2O3 or Al2O3, as well as three types of pellet catalysts V2O5–MoO3–WO3–Al2O3 and V2O5–MoO3–WO3–TiO2 were tested for comparison. The experiment results show that this catalyst has a higher catalytic activity for SCR with comparison to others. The results of characterization show, the preparation method of this catalyst can give rise to a higher BET surface area and pore volume, which is strongly related with the highly active performance of this catalyst. At the same time, the function of the combined carrier of TiO2/Al2O3 cannot be excluded.  相似文献   

6.
Composite types of TiO2–Al2O3 supports, which are γ-aluminas coated by titania, have been prepared by chemical vapor deposition (CVD), using TiCl4 as a precursor. Then supported molybdenum catalysts have been prepared by an impregnation method. As supports, we employed γ-alumina, anatase types of titania, and composite types of TiO2–Al2O3 with different loadings of TiO2. We studied the conversion of Mo from oxidic to sulfidic state through sulfurization by X-ray photoelectron spectroscopy (XPS). The obtained spectra unambiguously revealed the higher reducibility from oxidic to sulfidic molybdenum species on the TiO2 and TiO2–Al2O3 supports compared to that on the Al2O3 support. Higher TiO2 loadings of the TiO2–Al2O3 composite support led to higher reducibility for molybdenum species. Furthermore, the catalytic behavior of supported molybdenum catalysts has been investigated for hydrodesulfurization (HDS) of dibenzothiophene (DBT) and methyl-substituted DBT derivatives. The conversion over the TiO2–Al2O3 supported Mo catalysts, in particular for the 4,6-dimethyl-DBT, is much higher than that obtained over Al2O3 supported Mo catalyst. The ratio of the corresponding cyclohexylbenzene (CHB)/biphenyl (BP) derivatives is increased over the Mo/TiO2–Al2O3. This indicates that the prehydrogenation of an aromatic ring plays an important role in the HDS of DBT derivatives over TiO2–Al2O3 supported catalysts.  相似文献   

7.
Catalytic activities of Al2O3–TiO2 supporting CoMo and NiMo sulfides (CoMoS and NiMoS) catalysts were examined in the transalkylation of isopropylbenzene and hydrogenation of naphthalene as well as the hydrodesulfurization (HDS) of model sulfur compounds, conventional gas oil (GO), and light cycle oil (LCO). Al2O3–TiO2 supporting catalysts exhibited higher activities for these reactions except for the HDS of the gas oil than a reference Al2O3 supporting catalyst, indicating the correlation of these activities. Generally, more content of TiO2 promoted the activities. Inferior activity of the catalyst for HDS of the gas oil is ascribed to its inferior activity for HDS of dibenzothiophene (DBT) in gas oil as well as in model solvent decane, while the refractory 4,6-dimethyldibenzothiophene (4,6-DMDBT) in gas oil as well as in decane was more desulfurized on the catalyst. Characteristic features of Al2O3–TiO2 catalyst are discussed based on the paper results.  相似文献   

8.
The effect of a commercial Pt/Al2O3 catalyst on the oxidation by NO2 and O2 of a model soot (carbon black) in conditions close to automotive exhaust gas aftertreatment is investigated. Isothermal oxidations of a physical mixture of carbon black and catalyst in a fixed bed reactor were performed in the temperature range 300–450 °C. The experimental results indicate that no significant effect of the Pt catalyst on the direct oxidation of carbon by O2 and NO2 is observed. However, in presence of NO2–O2 mixture, it is found that besides the well established catalytic reoxidation of NO into NO2, Pt also exerts a catalytic effect on the cooperative carbon–NO2–O2 oxidation reaction. An overall mechanism involving the formation of atomic oxygen over Pt sites followed by its transfer to the carbon surface is established. Thus, the presence of Pt catalyst increases the surface concentration of –C(O) complexes which then react with NO2 leading to an enhanced carbon consumption. The resulting kinetic equation allows to model more precisely the catalytic regeneration of soot traps for automotive applications.  相似文献   

9.
Hong He  Changbin Zhang  Yunbo Yu 《Catalysis Today》2004,90(3-4):191-materials
The selective catalytic reduction (SCR) of NO by C3H6 in excess oxygen was evaluated and compared over Ag/Al2O3 and Cu/Al2O3 catalysts. Ag/Al2O3 showed a high activity for NO reduction. However, Cu/Al2O3 showed a high activity for C3H6 oxidation. The partial oxidation of C3H6 gave surface enolic species and acetate species on the Ag/Al2O3, but only an acetate species was clearly observed on the Cu/Al2O3. The enolic species is a more active intermediate towards NO + O2 to yield—NCO species than the acetate species on the Ag/Al2O3 catalyst. The Ag and Cu metal loadings and phase changes on Al2O3 support can affect the activity and selectivity of Ag/Al2O3 and Cu/Al2O3 catalysts, but the formation of enolic species is the main reason why the activity of the Ag/Al2O3 catalyst for NO reduction is higher than that of the Cu/Al2O3 catalyst.  相似文献   

10.
The effect of different chemical parameters on photocatalytic inactivation of E. coli K12 is discussed. Illumination was produced by a solar lamp and suspended TiO2 P-25 Degussa was used as catalyst. Modifications of initial pH between 4.0 and 9.0 do not affect the inactivation rate in the absence or presence of the catalyst. Addition of H2O2 affects positively the E. coli inactivation rate of both photolytic (only light) and photocatalytic (light plus TiO2) disinfection processes. Addition of some inorganic ions (0.2 mmol/l) like HCO3, HPO42−, Cl, NO3 and SO42− to the suspension affects the sensitivity of bacteria to sunlight in the presence and in absence of TiO2. Addition of HCO3 and HPO42− resulted in a meaningful decrease in photocatalytic bactericidal effect while it was noted a weak influence of Cl, SO42− and NO3. The effect of counter ion (Na+ and K+) is not negligible and can modify the photocatalytic process as the anions. Bacteria inactivation was affected even at low concentrations (0.2 mmol/l) of SO42− and HCO3, but the same concentration does not affect the resorcinol photodegradation, suggesting that disinfection is more sensitive to the presence of natural anions than photocatalytic degradation of organic compounds. The presence of organic substances naturally present in water like dihydroxybenzenes isomers shows a negative effect on photocatalytic disinfection. The effect of a mixture of chemical substances on photocatalytic disinfection was also studied by adding to the bacterial suspension nutrient broth, phosphate buffer and tap water.  相似文献   

11.
Catalytic reduction of NO by propene in the presence of oxygen was studied over SnO2-doped Ga2O3–Al2O3 prepared by sol–gel method. Although SnO2-doped Ga2O3–Al2O3 gave lower NO conversion than Ga2O3–Al2O3 in the absence of H2O, the activity was enhanced considerably by the presence of H2O and much higher than that of Ga2O3–Al2O3. The presence of SnO2 and Ga2O3–Al2O3 species having intimate Ga–O–Al bondings was found to be essential for the promotional effect of H2O. The promotional effect of H2O was interpreted by the following two reasons. The first one is the removal of carbonaceous materials deposited on the catalyst surface by H2O. The other is the selective inhibition by H2O of the reaction steps resulting in propene oxidation to COx without reducing NO.  相似文献   

12.
The nature of the silver phases of Ag/Al2O3 catalysts (prepared by silver nitrate impregnation followed by calcination) was investigated by X-ray diffractograms (XRD), transmission electron microscopy (TEM) and UV–VIS analyses and related to the activity of the corresponding materials for the oxidation of NO to NO2. The UV–VIS spectrum of the 1.2 wt.% Ag/Al2O3 exhibited essentially one band associated with Ag+ species and the NO2 yields measured over this material were negligible. A 10 wt.% Ag/Al2O3 material showed the presence of oxidic species of silver (as isolated Ag+ cations and silver aluminate), but the UV–VIS data also revealed the presence of some metallic silver. The activity for the NO oxidation to NO2 of this sample was moderate. The same 10% sample either reduced in H2 or used for the C3H6-selective catalytic reduction (SCR) of NO showed a significantly larger proportion of silver metallic phases and these samples displayed a high activity for the formation of NO2. These data show that the structure and nature of the silver phases of Ag/Al2O3 catalysts can markedly change under reaction feed containing only a fraction of reducing agent (i.e. 500 ppm of propene) in net oxidizing conditions (2.5% O2). The low activity for N2 formation during the C3H6-SCR of NO (reported in an earlier study) over the high loading sample can, therefore, be related to the presence of metallic silver, which is yet a good catalyst for NO oxidation to NO2. The reverse observations apply for the oxide species observed over the low loading sample, which is a good SCR catalyst but do not oxidize NO to NO2.  相似文献   

13.
Development of new catalysts for deep hydrodesulfurization of gas oil   总被引:3,自引:0,他引:3  
TiO2–Al2O3 composite supports have been prepared by chemical vapor deposition (CVD) over γ-Al2O3 substrate, using TiCl4 as the precursor. High dispersion of TiO2 overlayer on the surface of Al2O3 has been obtained, and no cluster formation has been detected. The catalytic behavior of Mo supported on Al2O3, TiO2 and TiO2–Al2O3 composite has been investigated for the hydrodesulfurization (HDS) of dibenzothiophene (DBT) and methyl-substituted DBT derivatives. The conversion over the Mo catalysts supported on TiO2–Al2O3 composite, in particular for the HDS of 4,6-dimethyldibenzothiophene (4,6-DMDBT) is much higher than that of conversion obtained over Mo catalyst supported on Al2O3. The ratio of the corresponding cyclohexylbenzenes/biphenyls is increased over Mo catalyst supported on TiO2–Al2O3 composite support. This means that the reaction rate of prehydrogenation of an aromatic ring rather than the rate of hydrogenolysis of C–S bond cleavage is accelerated for the HDS of DBT derivatives. The Mo/TiO2–Al2O3 catalyst leads to higher catalytic performance for deep HDS of gas oil.  相似文献   

14.
In situ Raman spectroscopy was used for studying the ternary 2% CrO3–6% V2O5/TiO2 catalyst, for which a synergistic effect between vanadia and chromia leads to enhanced catalytic performance for the selective catalytic reduction (SCR) of NO with NH3. The structural properties of this catalyst were studied under NH3/NO/O2/N2/SO2/H2O atmospheres at temperatures up to 400 °C and major structural interactions between the surface chromia and vanadia species are observed. The effects of oxygen, ammonia, water vapor and sulfur dioxide presence on the in situ Raman spectra are presented and discussed.  相似文献   

15.
The present paper gives a detailed review of the different studies under investigation in our laboratory concerning the use of TiO2 and TiO2–Al2O3 composites prepared by chemical vapor deposition (CVD) as support for sulfide catalysts in the HDS of dibenzothiophene (DBT) derivatives. The supports investigated here are: TiO2 (from Degussa, 50 m2/g), Al2O3 (Nikki, 186 m2/g) and TiO2–Al2O3 supports prepared by CVD of TiCl4 on alumina. Using several characterization techniques, we have demonstrated that the support composite presents a high dispersion of TiO2 over γ-Al2O3 without forming precipitates up to ca. 11 wt.% loading. Moreover, the textural properties of the support composite are comparable to those of alumina. XPS investigations of Mo and NiMo catalysts supported on the different carriers show that Mo-oxide species exhibit a higher degree of sulfidation on the surface of TiO2 and TiO2–Al2O3 than on alumina. The HDS tests of 4,6-DMDBT under mild operating conditions (573 K, 3 MPa) show that sulfide catalysts supported on the composite support (ca. 11 wt.%) are more active than those supported on to TiO2 or Al2O3. This higher HDS catalytic activity is attributed to the promotion of the hydrodesulfurization pathway, whereby the pre-hydrogenation of one of the aromatic rings adjacent to the thiophenic one may reduce the steric hindrance caused by the two methyl groups adjacent to the sulfur atom during the C–S bond cleavage.  相似文献   

16.
The effect of tungsten and barium on the thermal stability of V2O5/TiO2 catalyst for NO reduction by NH3 was examined over a fixed bed flow reactor system. The activity of V2O5/sulfated TiO2 catalyst gradually decreased with respect to the thermal aging time at 600 °C. The addition of tungsten to the catalyst surface significantly enhanced the thermal stability of V2O5 catalyst supported on sulfated TiO2. On the basis of Raman and XRD measurements, the tungsten on the catalyst surface was identified as suppressing the progressive transformation of monomeric vanadyl species into crystalline V2O5 and of anatase into rutile phase of TiO2. However, the NO removal activity of V2O5/sulfated TiO2 catalyst including barium markedly decreased after a short aging time, 6 h at 600 °C. This may be due to the transformation of vanadium species to inactive V–O–Ba compound by the interaction with BaO which was formed by the decomposition of BaSO4 on the catalyst surface at high reaction temperature of 600 °C. The addition of SO2 to the feed gas stream could partly restore the NO removal activity of thermally aged V2O5/sulfated TiO2 catalyst containing barium.  相似文献   

17.
李静  张启俭  齐平  韩丽  邵超 《工业催化》2017,25(6):19-23
二甲醚是一种理想的氢载体,可用于解决氢的储存和运输。以Pt/TiO_2为部分氧化催化剂,结合Ni/Al_2O_3重整催化剂,考察钛前驱体和焙烧温度对二甲醚部分氧化重整制氢反应的影响。结果表明,以Ti(C4H9O)4为原料制备的TiO_2为金红石相,Ti(SO4)2或Ti O(OH)2为原料制备的TiO_2为锐钛矿相;以Ti(C4H9O)4为原料制备的Pt/TiO_2-E催化剂催化性能略好,转化率接近100%,H2收率约90%,表明金红石相TiO_2负载的Pt催化剂略佳;以Ti(SO4)2为原料制备的Pt/TiO_2-S催化剂500℃焙烧可获得金红石相TiO_2。与Pt/Al_2O_3催化剂相比,Pt/TiO_2催化剂具有更好的催化性能,H2收率超过90%,而Pt/Al_2O_3催化剂H2收率约80%。  相似文献   

18.
The effect of additives on Pt-ZSM-5 catalysts was studied for the selective NO reduction by H2 in the presence of excess O2 (NO–H2–O2 reaction) at 100 °C. The reaction of NO in a stream of 0.08% NO, 0.28% H2, 10% O2, and He balance yielded N2 with less than 10% selectivity, which could not be increased by changing Pt loading or H2 concentration in the gas feed. Co-impregnation of NaHCO3 and Pt onto ZSM-5 decreased the BET surface area and the Pt dispersion. Nevertheless, the Na-loaded catalyst (Na-Pt-ZSM-5) exhibited the higher NOx conversion (>90%) and the N2 selectivity (ca. 50%). Such a high catalytic activity even at high Na loadings (≥10 wt.%) is completely contrast to other Na-added Pt catalyst systems reported so far. Further improvement of N2 selectivity was attained by the post-impregnation of NaHCO3 onto Pt-ZSM-5. In situ DRIFT measurements suggested that the addition of Na promotes the adsorption of NO as NO2-type species, which would play a role of an intermediate to yield N2. The introduction of Lewis base to the acidic supports including ZSM-5 would be applied to the catalyst design for selective NO–H2–O2 reaction at low temperatures.  相似文献   

19.
The effectiveness of Ag/Al2O3 catalyst depends greatly on the alumina source used for preparation. A series of alumina-supported catalysts derived from AlOOH, Al2O3, and Al(OH)3 was studied by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet–visible (UV–vis) spectroscopy, diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, O2, NO + O2-temperature programmed desorption (TPD), H2-temperature programmed reduction (TPR), thermal gravimetric analysis (TGA) and activity test, with a focus on the correlation between their redox properties and catalytic behavior towards C3H6-selective catalytic reduction (SCR) of NO reaction. The best SCR activity along with a moderated C3H6 conversion was achieved over Ag/Al2O3 (I) employing AlOOH source. The high density of Ag–O–Al species in Ag/Al2O3 (I) is deemed to be crucial for NO selective reduction into N2. By contrast, a high C3H6 conversion simultaneously with a moderate N2 yield was observed over Ag/Al2O3 (II) prepared from a γ-Al2O3 source. The larger particles of AgmO (m > 2) crystallites were believed to facilitate the propene oxidation therefore leading to a scarcity of reductant for SCR of NO. An amorphous Ag/Al2O3 (III) was obtained via employing a Al(OH)3 source and 500 °C calcination exhibiting a poor SCR performance similar to that for Ag-free Al2O3 (I). A subsequent calcination of Ag/Al2O3 (III) at 800 °C led to the generation of Ag/Al2O3 (IV) catalyst yielding a significant enhancement in both N2 yield and C3H6 conversion, which was attributed to the appearance of γ-phase structure and an increase in surface area. Further thermo treatment at 950 °C for the preparation of Ag/Al2O3 (V) accelerated the sintering of Ag clusters resulting in a severe unselective combustion, which competes with SCR of NO reaction. In view of the transient studies, the redox properties of the prepared catalysts were investigated showing an oxidation capability of Ag/Al2O3 (II and V) > Ag/Al2O3 (IV) > Ag/Al2O3 (I) > Ag/Al2O3 (III) and Al2O3 (I). The formation of nitrate species is an important step for the deNOx process, which can be promoted by increasing O2 feed concentration as evidenced by NO + O2-TPD study for Ag/Al2O3 (I), achieving a better catalytic performance.  相似文献   

20.
For almost a century vanadium oxide based catalysts have been the dominant materials in industrial processes for sulfuric acid production. A vast body of information leading to fundamental knowledge on the catalytic process was obtained by Academician [G.K. Boreskov, Catalysis in Sulphuric Acid Production, Goskhimizdat (in Russian), Moscow, 1954, p. 348]. In recent years these catalysts have also been used to clean flue gases and other SO2 containing industrial off-gases. In spite of the importance and long utilization of these industrial processes, the catalytic active species and the reaction mechanism have been virtually unknown until recent years.

It is now recognized that the working catalyst is well described by the molten salt/gas system M2S2O7–MHSO4–V2O5/SO2–O2–SO3–H2O–CO2–N2 (M=Na, K, Cs) at 400–600°C and that vanadium complexes play a key role in the catalytic reaction mechanism.

A multiinstrumental investigation that combine the efforts of four groups from four different countries has been carried out on the model system as well as on working industrial catalysts. Detailed information has been obtained on the complex and on the redox chemistry of vanadium. Based on this, a deeper understanding of the reaction mechanism has been achieved.  相似文献   


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