甲烷催化燃烧反应与甲烷传感器稳定性的研究

研究了甲烷催化燃烧反应活性及传感器稳定性的影响因素。结果表明,3％Pd／Al2O3催化剂具有较高的反应活性。催化剂、传感器结构、反应气体的传质过程和电桥的供电电压均影响传感器的稳定性。     

甲烷催化燃烧的实验研究

在含铂的Ｍｏｎｏｌｉｔｈ催化剂上进行了甲烷的催化燃烧反应。实验表明，室温下必须先用氢气来点火，甲烷才能催化燃烧。甲烷催化燃烧的允许工作温度为９００～１１００℃，过低的温度导至熄火，过高则会使铂催化剂失活。在实验的反应条件下，甲烷进料浓度范围很窄为４％—６％（体积）。为实现甲烷的稳定燃烧必须对反应条件提出较高的自动化要求     

用于甲烷燃烧的MnOx/La-Al2O3催化剂的研究

摘要:用La(NO3)3溶液等体积浸渍Al2O3颗粒制得了La-Al2O3,进行了比表面积测试、x-射线衍射(XRD)和红外光谱(FTIR)表征,考察了加入La对Al2O3结构和热稳定性的影响。以Al2O3、La-Al2O3为载体,Mn(CH3COO)2为前驱体,制备了MnOx/Al2O3、MnOx/La-Al2O3系列催化剂,进行了H2-程序升温还原(TPR)表征,测试了它们对甲烷燃烧的催化活性。结果表明:加入La提高了Al2O3的热稳定性,MnOx/La-Al2O3对甲烷燃烧的催化活性高于MnOx/Al2O3,La在La-Al2O3中的最佳加入量为5%(La原子占Al2O3的质量百分数)。     

甲烷催化燃烧用LaMn/Al_2O_3催化剂研究

为获得具有优良低温活性的甲烷燃烧用催化剂,采用稀土La作为助剂制备了系列Mn基催化剂,借助X射线衍射(XRD)、X射线光电子能谱(XPS)和程序升温还原(TPR)技术对催化剂的结构进行了表征,并评价了其对甲烷燃烧的低温催化性能。结果表明,La助剂的添加显著促进了活性组分MnO2的分散,使其更易于还原,且使Mn4+和晶格氧富集于催化剂表面,因而显著提高了催化剂对甲烷催化燃烧的低温活性。当La质量分数为5%时,催化活性最高,甲烷50%转化率对应的温度较未加助剂时降低了70℃,且完全转化的温度低至480℃。     

CrO_x/ZrO_2催化剂上甲烷催化燃烧性能

采用沉淀法制备了CrO_x/ZrO_2催化剂,考察800℃高温焙烧的CrO_x/ZrO_2催化剂对CH_4燃烧的催化性能。采用X射线衍射和拉曼光谱等技术对催化剂进行物相结构表征。结果表明,Cr物种以Cr_2O_3形式存在,随着焙烧温度升高,催化剂中ZrO_2和Cr_2O_3的晶粒明显增大。CrO_x/ZrO_2催化剂的比表面积大于相应的纯Cr_2O_3和ZrO_2。催化剂的CH_4燃烧活性随着Cr含量的增加而提高,Cr质量分数20%时活性最高,CH_4完全燃烧温度为450℃。     

辉光放电等离子体增强制备甲烷催化燃烧的高分散Pd/Al2O3催化剂

引　言催化反应在化学合成中占有极为重要的地位 [1] .最近 ,等离子体技术在催化剂制备领域的应用在发达国家受到广泛重视 [2～ 4 ] .利用等离子体技术制备的催化剂具有很多优点 ,例如大的比表面积、高分散性、晶格缺陷、活性组分单一等特性 .等离子体技术对催化剂表面改性可以     

甲烷催化燃烧催化剂催化理论与应用研究进展

概述了甲烷催化燃烧催化剂的研究现状,从组成甲烷燃烧催化剂的3个部分（基体、活性组分、氧化物载体）分别加以论述。通过掺杂一些金属和金属氧化物,不但可以提高高活性贵金属催化剂的热分解温度,还可以提高高温催化剂（如钙钛矿和六铝酸盐材料等）的催化活性。最后简要综述了甲烷催化燃烧反应机理。     

低浓度甲烷流向变换催化燃烧反应研究

将制备的整体式催化剂应用于小型流向变换催化燃烧反应系统上,在甲烷初始浓度为0.2%,气量为30 L·min-1,换向半周期为10 min的工况条件下考察了不同预热温度对甲烷催化燃烧活性的影响以及反应系统床层轴向温度分布情况。结果表明,随着预热温度升高,甲烷催化燃烧活性呈现升高的趋势,同时,在催化剂中添加助剂元素Pt可以提高催化剂催化活性;催化剂的预热温度对反应器床层温度分布影响较大,特别是反应系统的催化段。     

甲烷高温催化燃烧研究进展

甲烷催化燃烧具有环保、高效、节能等诸多优点,引起人们广泛的关注。综述了甲烷高温催化燃烧的研究现状,对甲烷燃烧催化剂材料的研究进展作了介绍,阐述了甲烷高温催化燃烧反应器的概况。     

辉光放电等离子体增强制备甲烷催化燃烧的高分散Pd/Al2O3催化剂

A novel Pd/Al₂O₃ catalyst prepared by glow discharge plasma technology is reported.The results of H₂-chemisorption indicate that palladium dispersion of the plasma-prepared Pd/Al₂O₃ reaches 29.7%,which is about 5 times higher than Pd/Al₂O₃ prepared by conventional preparation.Meanwhile,the particle diameter of the plasma-prepared catalyst is 3.8 nm, but the particle diameter of the conventional catalyst is 20.4 nm.Such plasma-prepared Pd/Al₂O₃ catalyst shows a higher activity for catalytic combustion of methane than the conventional catalyst.Methane conversion reaches 90% at 400 ℃, but it is only near 30% for the conventional catalyst at the same temperature.     

负载型钯催化剂上甲烷催化燃烧的研究进展

概述了负载型钯催化剂对甲烷完全氧化的催化机理,以及钯催化剂在甲烷催化燃烧中的性能特点。     

CO, H2 or C3H8 assisted catalytic combustion of methane over supported LaMnO3 monoliths

The effect of the addition of a second fuel such as CO, C₃H₈ or H₂ on the catalytic combustion of methane was investigated over ceramic monoliths coated with LaMnO₃/La-γAl₂O₃ catalyst. Results of autothermal ignition of different binary fuel mixtures characterised by the same overall heating value show that the presence of a more reactive compound reduces the minimum pre-heating temperature necessary to burn methane. The effect is more pronounced for the addition of CO and very similar for C₃H₈ and H₂. Order of reactivity of the different fuels established in isothermal activity measurements was: CO>H₂≥C₃H₈>CH₄. Under autothermal conditions, nearly complete methane conversion is obtained with catalyst temperatures around 800 °C mainly through heterogeneous reactions, with about 60–70 ppm of unburned CH₄ when pure methane or CO/CH₄ mixtures are used. For H₂/CH₄ and C₃H₈/CH₄ mixtures, emissions of unburned methane are lower, probably due to the proceeding of CH₄ homogeneous oxidation promoted by H and OH radicals generated by propane and hydrogen pyrolysis at such relatively high temperatures.

Finally, a steady state multiplicity is found by decreasing the pre-heating temperature from the ignited state. This occurrence can be successfully employed to pilot the catalytic ignition of methane at temperatures close to compressor discharge or easily achieved in regenerative burners.     

Metallic monolith supported LaMnO3 perovskite-based catalysts in methane combustion

Metallic monolith supported LaMnO₃ perovskite-based catalysts are characterized by a high activity in methane combustion (95.5% conversion at 745 °C) and by a high thermal resistance. The activity of the catalysts depends on the duration and temperature of LaMnO₃ calcination. The same relation holds for the chemical composition of the catalyst surfaces when they are determined by the XPS method. The shortening of the time of LaMnO₃ perovskite calcination from 12.5 h to 8 h (700 °C) reduces the conversion of methane over a fresh catalyst. This is attributable to the lower amount of manganese (Mn:La = 0.48) on the surface of this catalyst compared to the catalyst whose perovskite was calcined for 12.5 h (Mn:La = 1.8). The extension of calcination time from 8 h to 12.5 h (at 700 °C) brings about a decrease in the specific surface area (SSA) from about 13.7 m²/g to 9.4 m²/g. After approximately 6 h on stream, the activities of the two catalysts become comparable. Aging of the catalyst with an LaMnO₃ active layer at 920 °C for 24 h reduces methane combustion to 82.5% (at 745 °C). The aging process changes the catalyst surface, where Al and C content increases and the Mn:La ratio decreases. The activity of the monolithic LaMnO₃ catalyst rises with the increase in the amount of the active layer from 11.5% to 17.8%. Methane conversion is greater over catalysts with an LaMnO₃ than with an LaCoO₃ active layer, but the LaMnO₃ catalysts show a lower resistance to thermal shocks.     

Catalytic combustion of methane on novel catalysts derived from Cu-Mg/Al-hydrotalcites

Novel Cu-Mg/Al mixed oxides (designated as i-CMAO-800) were prepared by calcinations of Cu-Mg/Al hydrotalcites [(Cu²⁺ +Mg²⁺)/Al³⁺= 3] at 800 °C. Their performance for the catalytic combustion of methane was investigated. The oxides and their precursors were characterized by XRD, TG-DSC, TPR and N₂ adsorption/desorption techniques. The results showed that BET surface areas and the stability of the resultant oxides were greatly influenced by the copper contents in hydrotalcite precursors, bringing about difference in their activities for methane catalytic combustion. XRD results indicated that Cu was highly dispersed in hydrotalcite precursors in case of low copper contents, (Cu 40 wt%). For higher Cu contents, Cu(OH)₂ was formed, and, consequently, a separate phase of CuO was detected in the oxide catalysts after calcination. As indicated by the TG-DSC results, different decomposition behaviors were observed for various hydrotalcites. Thermal calcination promoted the formation of copper aluminates and segregation of CuO from the bulk phases. TPR results showed 15CMAO-800 has the highest reduction rate, and the catalytic activities of iCMAO-800 mixed oxides depend on both the reduction rates and the amounts of copper ions in mixed oxides. The catalyst 15-CMAO-800 showed the best performance.     

Ce改性Pd基整体式催化剂的结构特征及其甲烷催化燃烧性能

分别以拟薄水铝石和添加Ce的拟薄水铝石制备铝溶胶,经过堇青石（Cord）表面涂覆和Pd溶液浸渍,得到浸渍法和溶胶法Ce改性的Pd/γ-Al₂O₃/Cord整体式催化剂。采用XRD、SEM和XPS等对催化剂进行表征,评价其甲烷催化燃烧反应性能,并考察Ce的不同添加方式对催化剂结构和反应性能的影响。结果表明,适量Ce的添加可提高Pd基整体式催化剂的甲烷催化燃烧性能,溶胶法优于浸渍法。随着Ce添加量的增加,浸渍法改性的Pd基催化剂催化性能有所降低,溶胶法则呈现先升高后降低的趋势。溶胶法中Ce的添加物与γ-Al₂O₃涂层充分融合,提高了涂层的热稳定性和活性组分的分散度,0.5Pd/γ-Al₂O₃(3.0Ce)/Cord催化剂催化性能最优。     

Regeneration of S-poisoned Pd/Al2O3 catalysts for the combustion of methane

Regeneration of S-poisoned Pd/Al₂O₃ catalysts for the abatement of methane emissions from natural gas vehicles was addressed in this work.

Investigations were devoted to determine the temperature threshold allowing for catalyst reactivation under different CH₄ containing atmospheres. Under lean combustion conditions in the presence of excess O₂, partial regeneration took place only above 750 °C after decomposition of stable sulphate species adsorbed on the support. Short CH₄-reducing, O₂-free pulses led to partial catalyst reactivation already at 550 °C and to practically complete regeneration at 600 °C. Also in this case reactivation was associated with SO₂ release due to the decomposition of stable support sulphates likely promoted by CH₄ activation onto the reduced metallic Pd surface. Rich combustion pulses with CH₄/O₂ = 2 were equally effective to CH₄-reducing pulses in catalyst regeneration.

These results suggest that a regeneration strategy based on periodical natural gas pulses fed to the catalyst by a by-pass line might be efficient in limiting the effects of S-poisoning of palladium catalysts for the abatement of CH₄ emissions from natural gas engine.     

SrxCa1-xNiAl11O19催化剂的制备及其催化甲烷燃烧活性研究

用异丙醇盐水解法制备SrxCa1-xNiAl11O19(x=1.0,0.75,0.5,0.25,0)催化剂,通过X射线衍射、比表面积分析等实验技术及甲烷燃烧,对催化剂的结构和性质进行了考察。研究了掺杂不同量的钙离子对催化剂的结构以及对甲烷催化燃烧活性的影响。结果表明,催化剂在1 200℃焙烧后可以形成完整的六铝酸盐晶型,同时具有较高的催化性能和高温稳定性,不同量的Ca离子掺杂对于催化剂的比表面积有较大的影响。Sr0.25Ca0.75NiAl11O19催化剂具有较好活性,其起燃温度(T10%/℃)为590℃,完全转化温度(T90%/℃)为730℃。     

Methane catalytic combustion over Pd/Al2O3 in presence of sulphur dioxide: development of a regeneration procedure

Five different procedures (treatments with hydrogen, nitrogen, wet and dry air, and under vacuum) were tested for the regeneration of a partially deactivated alumina-supported Pd catalyst, used for the catalytic incineration of methane in presence of SO₂. The efficiency of these processes was evaluated considering the temperatures at which both, the catalysts deactivation, and the regeneration processes, took place. As general trend, hydrogen treatment is the best regeneration procedure, followed by treatment with wet air, whereas high deactivation temperatures lead to less efficient regeneration. The efficiency of the regeneration was observed to increase as regeneration temperature increases. These trends are discussed according to the results obtained in the characterisation of deactivated catalyst samples using TPR, TPO and TPD.