Lean NOxCatalysis over Sn/γ-Al2O3Catalysts

Sn/γ-Al₂O₃were effective and highly stable catalysts for NO reduction with propene under high partial pressures of oxygen and water. The activity depended on the Sn loading. For a 10 wt% Sn/Al₂O₃at 475–500°C, 58% conversion of 1000 ppm NO to N₂was obtained in the presence of 10% water and 15% O₂, at a space velocity of 30,000 h⁻¹, and 77% conversion at 15,000 h⁻¹. The NO conversion increased with O₂partial pressure but was suppressed by water below 500°C. The activity was also suppressed by SO₂but could be restored slowly after the removal of SO₂.     

Macroporous Monolithic Pt/γ-Al2O3 and K–Pt/γ-Al2O3 Catalysts Used for Preferential Oxidation of CO

Macro-porous monolithic γ-Al₂O₃ was prepared by using macro-porous polystyrene monolith foam as the template and alumina sol as the precursor. Platinum and potassium were loaded on the support by impregnation method. TG, XRD, N₂ adsorption–desorption, SEM, TEM, and TPR techniques were used for catalysts characterization, and the catalytic performance of macro-porous monolithic Pt/γ-Al₂O₃ and K–Pt/γ-Al₂O₃ catalysts were tested in hydrogen-rich stream for CO preferential oxidation (CO-PROX). SEM images show that the macropores in the macro-porous monolithic γ-Al₂O₃ are interconnected with the pore size in the range of 10 to 50 μm, and the monoliths possess hierarchical macro-meso(micro)-porous structure. The macro-porous monolithic catalysts, although they are less active intrinsically than the particle ones, exhibit higher CO conversion and higher O₂ to CO oxidation selectivity than particle catalysts at high reaction temperatures, which is proposed to be owing to its hierarchical macro-meso(micro) -porous structure. Adding potassium lead to marked improvement of the catalytic performance, owing to intrinsic activity and platinum dispersion increase resulted from K-doping. CO in hydrogen-rich gases can be removed to 10 ppm over monolithic K–Pt/γ-Al₂O₃ by CO-PROX.     

Gas-phase dehydration of glycerol over commercial Pt/γ-Al2O3 catalysts

Gas-phase dehydration of glycerol to produce acrolein was investigated over commercial catalysts based onγ-Al2O3, viz. A-64, A-56, I-62, AP-10, AP-56, AP-64 and KR-104. To understand the effect of Cl?anions, HCl-impregnated sup-ports have been investigated in the dehydration reaction of glycerol at 375 °C. For comparison, various H-zeolites were also examined. It was found that the glycerol conversion over the solid acid catalysts was strongly dependent on their acidity and surface area. And the relationship between the catalytic activity and the acidity of the catalysts was discussed. The outstanding properties of Pt/γ-Al2O3 catalyst systems for the dehydration of glycerol were revealed. Pt/γ-Al2O3 catalyst (AP-64) showed the highest catalytic activity after 50 h of reaction with an acrolein selectivity of 65%at a conversion of glycerol of 90%. Based on these results, catalysts based onγ-Al2O3 appear to be most promising for gas phase dehydration of glycerol.     

Stability of Pt/γ-Al2O3 Catalysts in Model Biomass Solutions

The stability of a Pt/??-Al₂O₃ catalyst in liquid water and aqueous solutions of 5?wt% glycerol or sorbitol at 225?°C is examined using a variety of physicochemical methods. It is demonstrated that the presence of glycerol and sorbitol significantly reduces the hydration of ??-Al₂O₃ to form boehmite as compared to treatment in pure water. The stability against hydration increases with increasing carbon chain length. Treatment with polyol solutions also results in reduced agglomeration of supported metal particles. The prevention of boehmite formation and agglomeration of metal particles are attributed to the formation of carbonaceous species on the surface. In addition to these effects, the deposits block a considerable portion of active metal surface area. IR spectroscopic analysis indicates that dehydration reactions play an important role in the formation of the carbonaceous deposits. The present results illustrate that water and dissolved biomass compounds can strongly affect the stability of heterogeneous catalysts under reaction conditions.     

Porous Pt/γ-Al2O3 catalytic membrane reactors prepared using mesitylene solvated Pt atoms

The opportunity of using mesitylene solvated Pt atoms for the deposition of Pt catalyst on inorganic membranes is shown. The catalytic activity of the membrane reactor has been tested using the hydrogenation of benzene as model reaction. The performance of the membrane reactor has been compared with that of a conventional packed bed using -Al₂O₃ powder impregnated with Pt. The effect of the feeding configuration has been investigated, and the results show a membrane effect due to the different degrees of accessibility of pores of different size. For alumina powder we have obtained an activation energy of 12.9 kcal/mol, which well agrees with the data reported in literature. The membrane reactor, instead, exhibited an activation energy ca. 60% lower. The preliminary porometry results have shown a slight effect of the platinum deposition process on membrane permeability.     

O3/TiO2/γ-Al2O3/UV降解草酸

采用臭氧与TiO2/γ-Al2O2/UV联用技术对降解草酸进行研究.考察了进气流量、草酸初始浓度、催化剂投加量,pH值及温度等因素对草酸降解的影响.研究表明,在一定范围内,随着进气流量的增加、温度的升高都会促使草酸的降解速率加快;溶液pH值对催化臭氧化有比较重要的影响,pH值2时,草酸的去除率最高.     

CO hydrogenation on Co/γ-Al2O3 and CoRe/γ-Al2O3 studied by SSITKA

Co/γ-Al₂O₃ and CoRe/γ-Al₂O₃ catalysts have been studied by the steady-state isotopic transient kinetic analysis (SSITKA) technique. It was found that neither the CO partial pressure, the temperature nor the space velocity influences the in situ CO adsorption. The space velocity, H₂/CO ratio and temperature was found to affect the intrinsic activity ( ) slightly, while the total pressure and syngas partial pressure had only a negligible effect. The surface concentrations and coverages were, however, unaffected by the space velocity, temperature, total pressure, syngas partial pressure and H₂/CO ratio. All changes, however, affected the methane selectivity, indicating that the methane selectivity was not a function of the surface inventory of methane precursors.     

O3/TiO2/γ-Al2O/UV降解草酸

采用臭氧与TiO2/γ-Al2O/UVV联用技术对降解草酸进行研究。考察了进气流量、草酸初始浓度、催化剂投加量、pH值及温度等因素对草酸降解的影响。研究表明,在一定范围内,随着进气流量的增加、温度的升高都会促使草酸的降解速率加快;溶液pH值对催化臭氧化有比较重要的影响,pH值2时,草酸的去除率最高。     

Strong improvement on CH4 oxidation over Pt/γ-Al2O3 catalysts

A very strong promotion effect of the presence of 1000 ppmV C₃H₈ in the reaction feed on CH₄–O₂ reaction was found over unsulfated 1%Pt/γ-Al₂O₃ catalyst. This promotion was further increased on pre-sulfated 1%Pt/γ-Al₂O₃. The promoting effect of pre-sulfation on the activity of 1%Pt/γ-Al₂O₃ for propane combustion results in a further improvement on methane combustion due to propane combustion heat which is generated at lower temperatures, activating methane combustion over pre-sulfated 1%Pt/γ-Al₂O₃ at even lower temperatures relative to unsulfated 1%Pt/γ-Al₂O₃. These results suggest that small amounts of propane in the gas feed during CH₄–O₂ reaction over a pre-sulfated Pt/γ-Al₂O₃ catalyst may eliminate methane emissions at low temperatures from lean-burn NGV exhausts without being deactivated by sulfur poisoning as Pd supported catalysts.     

肉桂醛在γ-Al2O3、La2O3和La2O3/γ-Al2O3表面吸附的红外光谱分析

利用傅立叶变换红外光谱,研究真空条件(87.78 kPa,353 K)下肉桂醛在γ-Al2O3、La2O3和La2O3/γ-Al2O3样品表面的吸附情况,并根据文献归属了肉桂醛吸附在这些氧化物表面的红外吸收峰.结果表明,肉桂醛在氧化物表面产生多部位吸附.吸附在La2O3/γ-Al2O3样品的肉桂醛分子的1 496 cm...     

VOCs催化燃烧催化剂Mn/γ-Al2O3和CuMn/γ-Al2O3的性能研究

用浸渍法制备了两种负载型的Mn/g -Al2O3和Cu-Mn/g-Al2O3复合氧化物催化剂,同时用共沉淀法制备了Cu-Mn-O复合氧化物催化剂。以气相色谱为检测手段,用常压气体流动评价装置考察了这三种催化剂对苯、甲苯、二甲苯等挥发性有机化合物VOCs的催化燃烧性能。发现负载型的催化剂转化率达到99%时的反应温度比非负载型的降低30~40C,其中Cu-Mn/g-Al2O3催化剂具有更好的低温活性,催化燃烧反应的速率明显提高。负载型催化剂表面的活性组分以高度分散状态存在和催化剂高的比表面积是性能好的主要原因。     

Neopentane conversion over Pd/γ-Al2O3

X-ray diffraction showed that during high temperature reduction at 600°C, chlorine-free Pd/-Al₂O₃ undergoes partial transformation to a Pd-Al alloy, which confirms results of other studies [9]. This evolution appears to have a large effect on the catalytic behaviour in the reaction of neopentane with hydrogen: the selectivity towards isomerization increases from <20 up to 80%. At the same time, the activation energy drops from 60 to 22 kcal/mol. These changes can be reversed by oxidation at 500°C followed by reduction at 300°C. The presence of residual chlorine (ex-PdCl₂ precursor) appears to inhibit the Pd induced reduction of Al₂O₃ leading to Pd-Al alloy formation.     

NO在Pt/γ-Al2O3上催化氧化反应机理和动力学

用连续流动管式反应器考察了在空时为0.090～0.720 s、NO进口浓度为0.03%～0.2%(体积分数)、O₂浓度为2%～10%(体积分数)和温度为473～573 K条件下,NO在Pt/γ-Al₂O₃上的催化氧化反应。结果表明：在空速为5000 h^-1、NO进口浓度为0.05%和O₂浓度为5%条件下,当反应温度从473 K依次升高到523 K和573 K时,NO催化氧化反应的定态转化率从22.4%提高到45.5%和74.3%。NO定态转化率随空时或O₂浓度的增加而增加,但基本与NO的进口浓度无关。基于实验结果和反应动力学理论,提出了含有6对12个正、逆向基元反应的机理,进而确立了以气相NO与解离吸附在催化剂表面的O之间的反应为控制步骤的NO催化氧化总反应速率模型,以其拟合动力学实验数据,确定了动力学参数,得到反应的活化能为80.01 kJ·mol^-1。     

Ni对Pt/γ-Al2O3催化甲基环己烷脱氢性能的影响

采用饱和浸渍法制备了γ-Al₂O₃负载的Pt单金属和Pt-Ni双金属催化剂,用固定床反应器评价了催化剂的甲基环己烷脱氢反应性能,以考察Ni对Pt/γ-Al₂O₃催化甲基环己烷脱氢性能的影响。结果表明,与单金属催化剂相比,Pt-Ni双金属催化剂具有更好的脱氢活性和稳定性。氢氧滴定分析结果表明加入Ni后Pt的分散性能变好,TEM分析表明加入Ni后金属颗粒尺寸变大,结合氢氧滴定与TEM数据,认为掺入Ni之后形成了Pt-Ni新的体系,此体系提高了催化剂表面上氢的结合能,最终提高了Pt-Ni双金属催化剂的脱氢活性和稳定性。此结果为开发适用于有机液体储氢材料脱氢的高效催化剂提供了思路。     

CuO/NiO/γ-Al2O3催化剂合成环己胺

以磷酸预处理的γ-Al2O3为载体,二次浸渍CuO／NiO活性组分制备催化剂,用于环己醇合成环己胺的临氢氨解反应。实验考察了催化剂的制备因素及反应条件对催化反应性能的影响．在反应温度190℃、压力0．8MPa、液时空速0．3h^-1、氨与环己醇的摩尔比为8时,环己醇的转化率为99％,环己胺的选择性达到95％。     

水热法制备γ-Al2O3粉体

本研究以氢氧化钠和氢氧化铝为原料,采用水热法对氧化铝的生长条件进行调控,得到结晶好,分布均匀,分散性高的γ-Al_2O_3粉体。主要探究前驱体陈化时间、溶液pH值、水热温度对氧化铝形貌与晶型的影响。SEM分析结果表明:陈化时间为0.5 h,溶液为pH=10,水热温度为250℃,可得到平均粒径2 um左右,表面光滑,分散性较好的条状γ-Al_2O_3氧化铝粉体。     

K对Pt/γ-Al2O3催化剂制备邻苯基苯酚催化性能的影响

通过加入不同K助剂对0.5% Pt/γ-Al₂O₃催化剂进行改性,考察了其在由环己烯基环己酮脱氢制邻苯基苯酚（OPP）的催化反应中的催化性能,利用XRD、H₂-TPD、NH₃-TPD、CO₂-TPD等手段对催化剂进行表征,并与反应结果关联。研究表明,Pt/γ-Al₂O₃催化剂加入K助剂后不同程度地减少了催化剂表面的酸、碱量和对氢的吸附量;采用6.00%K₂SO₄作为助剂,明显地弱化了催化剂表面的强酸和强碱中心,减少了酸、碱量,调整了催化剂表面对中间产物、OPP和氢吸附量,抑制了副反应,可显著提高生成OPP的选择性,在LHSV 0.12 h^-1、H₂空速33 ml·g^-1·h^-1、380℃的反应条件下,环己烯基环己酮转化率为100%,OPP选择性达90%以上。     

Ru-La2O3/γ-Al2O3催化CO选择性氧化反应

采用浸渍法制备了Ru-La2O3/γ-Al2O3复合氧化物催化剂,在固定床微反装置中考察了催化剂中稀土La的掺杂量、氧气量、原料气中水和CO2含量以及空速等工艺条件对Ru-La2O3/γ-Al2O3催化剂在CO选择性氧化反应中催化性能的影响.结果表明,Ru/γ-Al2O3催化剂添加质量分数10%的La2O3后的催化性能较好,且具有较好到抗湿性和抗CO2能力.在原料气组成为65%H2,25%CO2,1%CO,9%He,氧气的分压与CO分压相等,气体流速为100 mL/min和气体空速为10 000 h-1的条件下,在110～170℃进行CO选择性氧化,CO转化率大于99%,CO的出口浓度小于100 μL/L,满足了质子交换膜燃料电池对富氢气体中CO浓度的要求.     

KF/K2CO3/γ-Al2O3催化合成肉桂酸

以苯甲醛和丙二酸为原料,KF/K2CO3/γ-Al2O3为催化剂,经Knoevenagel反应,在无溶剂条件下催化合成了肉桂酸。产品用IR、1HNMR及元素分析进行表征。考察了催化剂用量、苯甲醛与丙二酸摩尔比和反应时间对肉桂酸收率的影响。结果表明:KF/K2CO3/γ-Al2O3具有良好的催化活性,较佳工艺条件为:苯甲醛10.2 mL(10.6 g,0.1 mol),n(苯甲醛)∶n(丙二酸)=1∶1.15,催化剂KF/K2CO3/γ-Al2O3用量2.5 g(含KF4.68 mmol),反应60 min,肉桂酸的平均收率达到92%以上。     

镍对Pt/γ-Al2O3催化剂稠环芳烃选择性加氢性能的影响

分别以氯铂酸和硝酸镍为铂和镍前驱体,通过等体积浸渍法制备了系列镍修饰的Pt/γ-Al₂O₃催化剂,并采用电感耦合等离子体原子发射光谱（ICP-AES）、氨程序升温脱附（NH₃-TPD）、氢气程序升温还原（H₂-TPR）、氢气程序升温脱附（H₂-TPD）及氢氧滴定法（H₂-O₂）等手段进行表征。以重整C₁₀⁺重芳烃为原料,在30 mL固定床装置上考察镍引入对Pt/γ-Al₂O₃催化剂稠环芳烃（PAHs）选择性加氢性能的影响。固定床评价结果表明,随镍含量增加,稠环芳烃加氢活性和单环芳烃选择性呈现先增加后降低的趋势,当0.1Pt/γ-Al₂O₃催化剂中引入0.5%（质量分数）的镍时,催化剂稠环芳烃加氢活性和选择性最佳,此时稠环芳烃转化率为75%左右,单环芳烃选择性为98%以上。结合H₂-TPR、H₂-TPD及H₂-O₂滴定等表征结果,分析主要原因在于一定量镍的引入提高了铂的分散度,同时由于铂的加氢活化能较低,铂通过溢流活化的氢迁移至非贵金属镍上,提高了金属镍的加氢性能。此外,铂的存在还可避免镍形成尖晶石结构等非活性相,促进镍氧化物的还原,进而提高了催化剂的稠环芳烃加氢活性、选择性和稳定性。