Al2O3负载Pt催化剂的合成及其甲醇低温催化燃烧性能研究

采用一步合成法制备了Al₂O₃负载Pt催化剂Pt/Al₂O₃,以甲醇催化燃烧作为目标反应研究了其催化性能,考察了还原剂浓度、表面活性剂用量、表面活性剂浓度和煅烧温度对Pt/Al₂O₃甲醇低温催化燃烧性能的影响。结果表明,当还原剂浓度为0.1 mol/L、表面活性剂(CTAB)用量为8.53 g/g_cat.、表面活性剂浓度为0.1 mol/L、煅烧温度为600℃时,所得催化剂的活性最高,25℃下甲醇催化燃烧的转化率达到52%。而改进一步合成法制备的负载型催化剂Pt/Al₂O₃具有更高的甲醇催化燃烧活性,25℃下甲醇催化燃烧的转化率为84%。     

OMS-2/Al2O3/堇青石整体式催化剂的制备及其催化性能研究

以Al₂O₃/堇青石蜂窝陶瓷为载体,氧化锰八面体分子筛(OMS-2)为活性组分,采用涂覆法制备了系列整体式催化剂。考察了黏合剂种类和活性组分涂覆次数对二甲醚(DME)催化燃烧性能的影响,并对催化剂进行XRD、BET、SEM、H₂-TPR、O₂-TPD等表征。结果表明,以甲氧基聚乙二醇为黏合剂经一次涂覆制备的整体式催化剂的性能最佳,活性组分OMS-2以相互交织的簇体均匀分布在载体上,并与Al₂O₃之间存在较强的相互作用。涂层的添加有效增加了催化剂的比表面积,提高了催化剂的性能,最佳催化活性t₉₀为257 ℃。     

Ni/Al2O3催化甲烷裂解

分别通过浸渍法和共沉淀法制备了不同Ni负载量的Ni/Al2O3催化剂。考察了Ni负载量、制备方法以及反应温度对Ni/Al2O3催化甲烷裂解性能的影响。结果表明,在550℃,浸渍法制备的Ni/Al2O3催化剂,当Ni负载量为20%(质量分数)、Ni金属平均粒径为11.25 nm时,具有最佳的甲烷催化裂解效果,其每摩尔Ni的氢气产量和每克Ni碳产量分别为164 mol和15.30 g。催化剂制备方法对Ni/Al2O3甲烷催化裂解反应有显著影响,相同Ni负载量共沉淀法制备的Ni/Al2O3甲烷催化裂解总体效果要好于浸渍法制备的Ni/Al2O3,而且反应过程中生成的碳纤维较长,管径也较均一。550℃时,共沉淀法制备的Ni负载量为41.2%(质量分数)的Ni/Al2O3催化剂在反应至350 min时,仍保持着30%以上的转化率。     

单层分散CuOx对甲苯催化燃烧作用的研究

考察了一系列在不同温度下制备的Cu/Al2O3催化剂对苯催化燃烧的性能,并利用X-射线粉末衍射（XRD）、X-射线光电子能谱（XPS）、程序升温还原（TPR）对催化剂进行了表征．结果表明：低于单层分散的CuO具有可在低温还原的特性．在低于单层分散阈值的范围内,随着CuO负载量的增加催化剂活性加．超过单层分散阈值,催化剂...     

CO oxidation over Co3O4/SiO2 catalysts: Effects of porous structure of silica and catalyst calcination temperature

The catalytic performances of Co3O4/SiO2 catalysts prepared by incipient wetness impregnation for CO oxidation were investigated using three kinds of silica as carriers with different pore sizes of 7.7, 14.0 and 27.0 nm. The effects of calcination temperature on the catalyst surface and micro structure properties as well as catalytic performance for the oxidation of carbon monoxide were also studied. All catalysts were characterized by N2 adsorption-desorption, XRD, XPS, FTIR, H2-TPR and O2-TPD. It was found that the properties and crystal size of cobalt-containing species strongly depended on the pore size of silica carrier. While the silica pore size increased from 7.7 to 27.0 nm, the Co3O4 crystal size increased from 8.5 to 13.5 nm. Moreover, it was demonstrated that if the spinel crystal structure of Co3O4 was obtained at a calcination temperature as low as 150 ℃, the catalyst sample would have a high Co3O4 surface dispersion and a increase of surface active species, and thus exhibit a high activity for the oxidation of carbon monoxide.     

Sulfuration of Pt/Al2O3, Pt?Re/Al2O3 and Pt?Ir/Al2O3 catalysts

Three reforming catalysts Pt/Al₂O₃, Pt–Ir/Al₂O₃ and Pt–Re/Al₂O₃ have been sulfurated by H₂S and tested by their activities in benzene hydrogenation. By treatment at 500°C under hydrogen flow only a part of the initial activity of the non-sulfurated catalyst is retained. So only a part of the adsorbed sulfur is easily removed in these conditions. The remaining sulfur for each of the catalysts (Pt/Al₂O₃, Pt–Ir/Al₂O₃ and Pt–Re/Al₂O₃) gives the same atomic ratio of 0.5 sulfur atom per accessible metallic atom.

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Pt/Al₂O₃, Pt–Ir/Al₂O₃ Pt–Pe/Al₂O₃ . 500°C H₂ . . ., . (Pt/Al₂O₃, Pt–Ir/Al₂O₃ Pt–Pe/Al₂O₃) 0,5.

     

Kinetics of methane combustion on Fe2O3/TiO2 catalysts

The objective of this work was to study the kinetics of methane combustion for a series of Fe₂O₃/TiO₂ catalysts. An increase in activity is observed as iron loading increases, and can be attributed to an increase of surface coverage by Fe₂O₃ species. Kinetic studies revealed that the reaction orders with respect to methane, oxygen, carbon dioxide and water are 1, 0, 0 and -1 respectively. This revised version was published online in June 2006 with corrections to the Cover Date.     

Ru-Ni/Al2O3催化马来酸二甲酯加氢性能研究

以Al₂O₃为载体,RuCl₃·xH₂O及Ni（NO₃）₂·6H₂O为活性组分前驱体,采用吸附-沉淀法制备系列Ru-Ni/Al₂O₃催化剂,以马来酸二甲酯（DMS）催化加氢为探针反应,考察了活化条件和Ni的添加量对催化剂性能的影响。随Ni负载量的升高,Ru-Ni/Al₂O₃催化剂活性呈现先升高后降低的趋势,在Ni：Ru的原子比为6：1时（催化剂Ru₁Ni₆/Al）催化活性最高。催化剂Ru₁Ni₆/Al在氢气中200 ℃直接还原后的平均转化率与氢气中400 ℃还原后的平均转化率接近,达到了单组分Ru/Al催化剂的1.5倍以上。XPS、XRD、H₂-TPR数据表明,Ru与Ni之间发生了较强的相互作用,Ni的加入促进了金属Ru在载体上的分散,提高了催化活性。     

镁助剂改性Pd/Al_2O_3甲烷催化燃烧催化剂:Mg/Al物质的量比对催化剂载体及活性物种形成的影响

本文研究了系列不同含量镁助剂改性的Pd/Al_2O_3催化剂的甲烷催化燃烧反应。研究表明,随着镁添加量的增加,载体由Al_2O_3转变为尖晶石型MgAl_2O_4,进一步增加Mg/Al物质的量比至3∶1时,形成了Mg(Al)O_x固溶体;催化剂中活性相Pd物种以金属Pd,PdO_x或Pd-载体复合氧化物形式存在,各物种的相对含量以及Pd?PdO间的转化能力存在一定的差异。PdO_x物种表现为具有较高的低温活性,而金属Pd和Pd-载体复合氧化物的高温活性较好。当Mg/Al物质的量比为1∶3时,催化剂的Pd?PdO转化能力最强,表现出了最高的甲烷催化燃烧反应活性。     

纳米片聚结Co3O4微球催化甲苯燃烧

采用乙二胺辅助的水热法制备了纳米片聚结的Co₃O₄微球. 利用多种分析技术表征了其物化性质,并评价了其对甲苯燃烧的催化活性. 结果表明,由添加1.0 ml乙二胺经140 ℃水热处理12 h后制得的Co₃O₄样品呈纳米片聚结的微球状表面形貌. Co₃O₄微球样品的比表面积约为66 m² g^-1. 与体相Co₃O₄样品相比,Co₃O₄微球样品具有较高的氧吸附物种浓度和较好的低温还原性. 当空速为20000 ml g^-1 h^-1时,在Co₃O₄微球样品上甲苯转化率达到50%和90%时的反应温度分别为230和254 ℃. 这与该样品具有较大的比表面积、较高的氧吸附物种浓度和较好的低温还原性相关.     

TiO_2掺杂CuMnCe/Al_2O_3催化剂对甲烷催化燃烧脱氧反应的影响

以掺杂了不同TiO_2含量的Al_2O_3作为载体,通过等体积浸渍法制备了一系列不同TiO_2含量的CuMnCe/TiO_2-Al_2O_3催化剂,用BET、H_2-TPR、XRD和XPS表征技术对催化剂物理化学性质进行表征,并考察了催化剂在含甲烷气脱氧反应中的催化性能。结果表明,在载体中添加TiO_2对催化剂活性组分的晶相结构和分散度没有明显影响;但有效改善了Al_2O_3载体抗烧结能力;增加了CuMnCe/Al_2O_3催化剂表面Ce~(3+)/(Ce~(3+)+Ce~(4+))的相对含量,从而提高了活性氧的移动性,且使催化剂表面可氧化还原物种含量和表面吸附氧Osur/(Osur+Olatt)的含量增多。有效改善了催化剂在含甲烷气催化燃烧脱氧上的催化活性。其中,CuMnCe/4%TiO_2-Al_2O_3表现出最优的催化活性,在387℃时可使含甲烷气中氧气的转化率达到100%。     

Effect of water in the precursor solution on the catalytic property of LaMnAl11O19 high temperature combustion catalyst

Manganese-substituted lanthanum hexaaluminates were prepared by the sol-gel method. The effect of water content on the catalyst preparation was examined. Large water content caused a rapid decrease in the surface area. When the R (R is the mole ratio of H₂O/ Al(OC₃H₇)₃) is equal to 1.5, the catalyst retains a specific surface area of 13.5 m² g⁻¹ and shows higher activity in CH₄ combustion.     

Toluene methylation on AlPO4-Al2O3 catalysts (5–15 wt.% Al2O3)

The alkylation of toluene with methanol over AlPO₄-Al₂O₃ (5–15 wt.% Al₂O₃) catalysts produces a mixture of xylenes (XYL) although trimethylbenzenes (TMB) were also found. The TMB selectivity increased with temperature at the expense of XYL selectivity. Isomer distribution was approximately 48, 24 and 27 mol% foro-, m- andp-XYL, and 74, 26 and 0 mol% for 1,2,3-, 1,2,4- and 1,3,5-TMB, both quite different from the equilibrium isomer composition. The catalytic activity increased with alumina content, however, it decreased on increasing the calcination temperature in the 923–1273 K range. Good correlations between catalytic activity and the increase in acidic properties with Al₂O₃ loading (as determined by base chemisorption, in the gas phase,versus pyridine and 2,6-dimethylpyridine) have been obtained.     

Kinetics of Co?Mo/Al2O3 catalyst reduction

According to kinetic studies on the reduction of commercial Co–Mo/Al₂O₃ and model catalysts in H₂ at 523–773 K, the kinetic curves for the reduction process have been determined. The reduction rate is shown to be higher for the commercial catalyst. Activation energies E_act for the reduction of several forms of Mo and Co in Co–Mo/Al₂O₃ catalysts are presented.

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H₂ 523–773 . , : Mo Co .

     

等离子体改性CuO/γ-Al_2O_3催化剂催化低浓度甲烷燃烧性能

为了研究CuO/γ-Al_2O_3催化低浓度甲烷燃烧性能,采用普通浸渍法和低温等离子体改性的方法分别制备了CuO/γ-Al_2O_3和CuO/γ-Al_2O_3-P催化剂,并用于低浓度甲烷燃烧,考察了Cu负载量和等离子体改性工艺对其催化活性的影响。结果表明,Cu负载量为7%时,催化剂的活性最强。改性气体、气体空速、放电电压、放电频率、等离子体处理时间均是影响催化剂活性的因素。氧气适合用作催化剂的改性气体,而氮气不宜作为改性气体使用。氧气作为改性气体时,最佳的改性工艺条件为峰峰值电压45 kV、放电频率14.71 kHz、等离子体处理时间30 min、氧气空速20 mL/(min·g)。在此工艺条件下制备的催化剂用于低浓度甲烷催化燃烧,可使t10降低23℃、t50降低6℃、t90降低19℃,同时,可使反应的活化能由79.27 kJ/mol降低为76.12 kJ/mol。催化剂的SEM、BET、XRD、XPS、H_2-TPR表征结果表明,等离子体对催化剂的改性作用主要在于增大了催化剂的比表面积、促使催化剂中Cu周围电子云密度降低及体相氧向表面氧迁移,从而利于甲烷在催化剂表面的吸附、活化和转化。     

Selective Catalytic Reduction of NO with Propene over Au/Fe2O3/Al2O3 Catalysts

A series of Au/Fe₂O₃/Al₂O₃ catalysts were prepared by the homogeneous deposition-precipitation method. The catalytic activity of the catalyst samples for selective catalytic reduction of NO by propene under oxygen-rich atmosphere was evaluated. The results showed that 2%Au/10%Fe₂O₃/Al₂O₃ exhibited good low-temperature activity. The maximum of NO conversion reached 43% at 300 °C, while it was only 21% over the 2%Au/Al₂O₃ catalyst at the same temperature. The addition of 2% steam to the feed gas had little effect on the catalytic activity. X-ray diffraction results indicated that both Au and Fe₂O₃ particles were highly dispersed over Al₂O₃. H₂-temperature-programmed reduction results indicated that there was strong interaction between Au and Fe₂O₃, which made the reduction of Fe₂O₃ easy. The synergistic effect between Au and Fe₂O₃ was probably responsible for the good catalytic performance of the Au/Fe₂O₃/Al₂O₃ catalyst at low temperature.     

Sulfurization of Pt/Al2O3?Cl catalysts. IV. Adsorption sites of H2S on Al2O3, Al2O3?Cl and Pt/Al2O3?Cl

Chemisorption of H₂S on Al₂O₃, Al₂O₃–Cl and Pt/Al₂O₃–Cl has been studied by gravimetry and IR spectroscopy. The influence of the amount of Cl on the H₂S adsorption equilibrium value and the nature of the adsorption sites at low and high coverages are discussed.

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H₂S Al₂O₃, Al₂O₃–Cl Pt/Al₂O₃–Cl . Cl H₂S, .

     

CeO2-MnOx催化剂形貌对低浓度甲烷催化燃烧反应性能的影响

采用水热合成法制备了船形、扁球形及纳米片CeO₂-MnO_x复合氧化物。并运用低温N₂吸脱附、XRD、SEM、TEM、H₂-TPR、拉曼光谱、XPS等表征技术对不同形貌CeO₂-MnO_x复合氧化物的结构与其低浓度CH₄催化燃烧反应性能之间的关系进行了关联。结果表明,CeO₂-MnO_x复合氧化物的形貌与其催化性能密切相关。其中,扁球形CeO₂-MnO_x复合氧化物的氧空位、Ce³⁺含量及表面吸附活性氧物种最多,其CH₄催化燃烧反应活性最高,540℃时,可将CH₄完全转化;其次是船形CeO₂-MnO_x复合氧化物催化剂,540℃时其CH₄转化率为94.05%;与前两者相比,纳米片CeO₂-MnO_x复合氧化物催化剂的氧空位及表面吸附活性氧物种较少,活性较差,相同反应温度下,其CH₄转化率仅为89.68%。     

丙烷在Ce-Fe/Al2O3/cordierite上选择性催化还原NO

利用凝胶溶胶法和浸渍法制备了Ce-Fe/Al₂O₃/cordierite催化剂,实验研究了其催化丙烷选择性还原NO的特性。结果表明,当铈的负载量从1%增加至5%时,Ce-Fe/Al₂O₃/cordierite的C₃H₈-SCR性能先增强后减弱,3.5Ce-Fe/Al₂O₃/cordierite具有最佳的脱硝性能,在有氧条件下,600℃时可实现96.5%的脱硝效率。Ce的加入能够提升Fe/Al₂O₃/cordierite催化剂的抗硫性能。烟气中通入0.02%的SO₂后,3.5Ce-Fe/Al₂O₃/cordierite催化丙烷还原NO的转化率始终维持在93%,而没有经过Ce修饰的Fe/Al₂O₃/cordierite的NO转化率从88%下降为80%左右。利用XRD、N₂吸附-脱附、SEM、H₂-TPR、吡啶吸附红外光谱等手段研究了催化剂的物理化学性质。结果表明,加入助剂铈能与Fe形成了固溶体,增加催化剂表面Lewis酸浓度和氧化还原能力,从而提高了催化丙烷还原NO的性能。过多的铈引入会减少Fe₂O₃结晶体的形成,不利于在C₃H₈-SCR反应中形成NO₂/NO₃^-物种,从而导致NO还原效率下降。     

超声改性的CuO/Al2O3-MgO催化剂结构 及其超低浓度甲烷催化燃烧性能

采用普通浸渍和超声改性的方法分别制备了CuO/Al₂O₃-MgO催化剂,用于超低浓度甲烷的催化燃烧,并利用SEM、XRD、XPS、H₂-TPR等技术对催化剂进行表征,研究了超声改性作用对催化剂的结构和性能的影响.结果表明,与普通浸渍法制备的催化剂相比,在超声改性的CuO/Al₂O₃-MgO催化剂上,甲烷的转化率得到提高,燃烧特征温度降低.随着超声时间的延长和超声功率的增加,催化剂的催化活性均呈现先增大后减小的趋势;催化剂制备的最佳超声工况为功率150 W、时间20 min.超声改性可使催化剂的比表面积和孔容积增大,表面催化活性较高的Cu⁺浓度增加,活性组分CuO由晶相向非晶相转变、分散度增大,晶粒粒径变小、分布更均匀;这使得甲烷催化燃烧的表观活化能下降、催化剂活性得到增强.