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℃。     

甲烷催化燃烧用介孔ZrO2担载CuO催化剂

以介孔ZrO2为载体,采用湿式浸渍法制备了担载型铜基催化剂,以甲烷催化燃烧为模型反应考察了不同铜含量对催化剂结构和性能的影响,并采用N2吸附-脱附、程序升温还原 (TPR) 和X射线衍射 (XRD)等技术对催化剂进行了表征.结果显示CuO/ZrO2催化剂具有优良的甲烷催化燃烧性能;铜含量为5%质量分率的催化剂表现出最好的低温催化活性和优良的稳定性,甲烷转化率达到90 %时对应的反应温度 (T90) 低至358 ℃;若铜含量继续增加,活性组分CuO会发生聚集,导致催化剂的低温活性降低.     

低浓度甲烷在微小燃烧器中的催化燃烧实验

选用泡沫金属(Fe-Ni)作为催化剂载体, 通过浸渍法制备了整体式催化剂(Pd/Al₂O₃/Fe-Ni)。然后使用该泡沫金属载体整体式催化剂在微小燃烧器中对低浓度甲烷进行催化燃烧实验, 分析了燃烧器温度、甲烷浓度以及流量对甲烷转化率的影响。结果表明, 随着燃烧反应器内温度的升高, 混合气体总流量的降低和甲烷浓度的增大, 甲烷的转化率增大;进一步分析表明温度是影响转化率最关键的因素, 当燃烧反应器内温度为550℃, 甲烷浓度为5%, 总流量为50 ml·min^-1时, 甲烷的转化率可以达到98.7%。     

基于贵金属催化剂的低浓度甲烷催化燃烧实验研究

本文在自行搭建的催化燃烧实验台上,用贵金属催化剂进行了低浓度甲烷燃烧实验,研究了催化剂活性组分、催化剂载体、甲烷浓度、混合气流速和温度对甲烷转化率的影响。结果表明,钯-铑催化剂起燃温度最低为280℃,铂催化剂均在300℃以上。钯-铑催化剂的甲烷转化率最高可达90%,而铂催化剂最高仅为75%。因此,钯-铑催化剂更适合于甲烷催化燃烧。     

制备方法对双钙钛矿型催化剂性能的影响

采用溶胶-凝胶法、水热法、共沉淀法和溶胶-凝胶-水热联用法等方法制备了新型稀土钙钛矿型复合氧化物LaSrFeNiO₆,探究不同制备方法对催化剂催化甲烷燃烧性能的影响。通过BET、XRD、SEM、H₂-TPR、FT-IR和TG-DSC等技术对其进行物理性能表征及其催化甲烷燃烧活性测试。结果表明：在不同的制备方法下均可形成完整的双钙钛矿晶型，且不同制备方法下甲烷燃烧转化率和催化活性不同，其中溶胶-凝胶-水热联用法制备的催化剂下甲烷转化率最高，转化温度最低，起燃温度T_10%为355℃,T_90%为536℃。     

温度对水热合成制备LaMnO3催化剂的性能影响

以尿素水解为基础,采用水热合成法制备了一系列以Mn为活性组分的钙钛矿催化剂(LaMnO3),研究了反应温度对催化剂的热稳定性、比表面积及其催化甲烷燃烧性能的影响。结果表明,当前驱液温度为60℃,催化剂经700℃焙烧6 h后,甲烷转化率可达95%以上,比表面积为14.14 m2/g。     

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     

FCP-1型催化剂催化燃烧PTA尾气性能研究

研究了FCP-1催化剂对PTA尾气的催化燃烧性能。FCP-1催化剂对PTA尾气具有良好的催化燃烧活性,在反应温度280℃,PTA尾气的转化率可达98%以上,出口净化气中非甲烷总烃和苯满足国家排放标准;反应空速从23 000 h-1增加至50 000 h-1,FCP-1催化剂的活性基本保持不变,出口非甲烷总烃60 mg/m3,苯≤6 mg/m3:甲苯未检出;500 h的催化剂稳定性试验运行期间,出口非甲烷总烃60 mg/m3,苯7 mg/m3,甲苯10 mg/m3。     

催化燃烧法去除含氪气体中甲烷的实验研究

为制备满足放射性测量需求的Kr气体源,需对含Kr气体中的高浓度CH4进行初步分离,本文开展了催化燃烧法分离CH4和Kr的实验研究.研究结果表明,CH4的催化燃烧转化率随CH4浓度和催化温度的升高而增加,H2对CH4催化燃烧的抑制作用随着H2浓度的升高而变大,CO对CH4催化燃烧的抑制作用随着CO浓度的升高而变小,模拟气...     

载体及活性组分对甲烷低温燃烧催化性能的影响

以一定浓度的Pd为活性组分,-γA l2O3为载体,用浸渍法制备了甲烷低温燃烧催化剂,运用固定床反应装置着重研究载体对甲烷低温燃烧反应的催化性能的影响。同时采用同一种载体条件下,重点考察不同浓度的单一活性组分Pd或Pt和(Pt-Pd)双活性组分催化剂对甲烷低温燃烧反应的催化性能的影响。结果表明,由不同载体,负载同一浓度活性组份制备出的催化剂活性有较大差异。(Pt-Pd)/A l2O3双组分燃烧催化剂,性能优于单一组分的Pd/A l2O3或Pt/A l2O3催化剂,(Pd-Pt)/A l2O3体系具有较高的甲烷催化燃烧活性,催化燃烧的起燃温度最低。相比当(Pd 0.2%-Pt 0.1%)/A l2O3时催化剂活性最高,CH4转化率50%的温度为345℃,完全转化温度为405℃。通过1 000 h稳定性试验,显示出甲烷完全氧化温度为405℃左右,具有较好的低温活性及热稳定性。     

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。     

甲烷催化燃烧反应工艺研究进展

甲烷催化燃烧是一种清洁高效的甲烷燃烧技术,在节能减排中具有重要的应用价值。从催化剂、反应工艺和过程强化等方面对近年来甲烷催化燃烧技术进行综述,重点介绍颗粒催化剂固定床反应工艺、整体式催化剂反应工艺、流化床反应工艺和吸放热耦合反应工艺研究进展。用于固定床反应器的颗粒催化剂主要为负载型贵金属催化剂和非贵金属氧化物催化剂。贵金属催化剂活性好,起燃温度低,适合低浓度甲烷的催化燃烧。非贵金属氧化物催化剂耐高温性好,适合较高浓度甲烷燃烧体系。整体式催化剂的甲烷催化燃烧反应工艺中,最常用的是蜂窝陶瓷和金属合金等整体式催化剂的多段式催化燃烧反应器的设计。设计直接采用多段式整体催化剂,催化剂的位置不同,发挥的催化作用也不同。流化床催化燃烧装置具有燃烧过程接触面积广、热容量大和换热效率高等特点,可有效避免传统的固定床催化燃烧反应工艺存在的问题,非常适合应用于低浓度甲烷的催化燃烧过程。利用甲烷催化燃烧强放热的特点,将催化燃烧产生的热量进行时间或空间的耦合,可以开发出吸-放热耦合反应工艺。其中,固定床催化反应器中的流向变换强制周期操作作为一种高效的过程强化技术,在节约反应器成本的同时,可以提高反应热量的利用率。     

1kW SOFC-CHP系统用催化燃烧耦合蒸汽重整反应器的实验研究

针对1 kW 固体氧化物燃料电池热电联供(SOFC-CHP)系统开发了集成催化燃烧、换热及蒸汽重整的反应器,搭建了性能评价系统,系统研究了燃烧侧气体组分及工艺参数对该反应器性能的影响规律。实验结果表明:在反应器燃烧侧气体入口温度为300℃、空燃比为10:1、电堆燃料利用率为65%、水碳比为3 的条件下,重整侧转化率达到73.6%,重整尾气中H₂ 含量为67.5%。电堆燃料利用率对重整反应转化效率影响较大,其值大于80%时,采用尾气燃烧的余热回收方式无法有效为蒸汽重整提供所需热量。在150~350℃范围内,降低燃烧侧气体入口温度对重整反应效率影响较小,建议采用尾气先换热再进行催化燃烧的流程设计,保证重整效率的前提下可有效提升系统热效率。空燃比的降低可小幅度提升重整效率,在保证电堆反应温度稳定的前提下,适当降低空燃比可减少空气压缩机的功耗,从而提升整个系统的效率。研究成果对SOFC-CHP 系统的优化和整体效率提升具有指导意义。     

Catalytic combustion of coal mine ventilation air methane

Coal mine methane (CMM) is not only a greenhouse gas but also a wasted energy resource if not utilised. Underground coal mining is by far the most important source of fugitive mine methane, and approximately 70% of all coal mining related emissions are from underground ventilation air. Hence, research and development on mine methane capture, mitigation and utilisation should focus on methane emitted in ventilation air.To develop more efficient, cost effective technology for the mitigation and utilisation of mine ventilation air methane, this paper introduces the monolith catalyst bed reactor, which has better characteristics for power generation applications than fixed bed and fluidised bed reactors. This is due to its very low pressure drop at elevated mass throughputs, high geometrical area, and high mechanical strength and high resistance to dust. This paper briefly reviews methane catalytic combustion basics, and mainly presents experimental results on simulated ventilation air methane (VAM) catalytic combustion performance of four catalysts tested at different temperature, pressure and CH₄ concentrations. The experimental results show that determination of major operational parameters including temperature is very important for designing large-scale combustors to achieve high methane conversion rate. The major operational parameters determined in the experimental rig would be a reference for the design. In general, a preheated air temperature of ≥450 °C is required for the most effective of the four tested catalysts.     

新型催化材料Sr2FeMoO6的葡萄糖溶胶-凝胶法合成及甲烷催化燃烧性能

采用葡萄糖溶胶-凝胶法合成了Sr₂FeMoO₆催化剂,研究了空气、氩气和H₂/N₂ 3种焙烧气氛对产物的结构和性能的影响。运用X射线衍射（XRD）、程序升温还原（TPR）、傅里叶变换红外光谱（FT-IR）、比表面（BET）及磁性测量与甲烷催化燃烧活性评价等技术对所制备的样品进行了表征。XRD实验结果表明,H2/N2气氛下焙烧得到的样品是单相的双层钙钛矿结构氧化物Sr₂FeMoO₆,在氩气下焙烧的样品形成了主相为双层钙钛矿结构氧化物Sr₂FeMoO₆,同时伴有少量的SrMoO₄相,但在空气下焙烧的样品中除了Sr₂FeMoO₆的衍射峰,还出现了强度很高的SrMoO₄相的衍射峰。从TPR、FT-IR和磁性表征结果发现,不同的焙烧气氛所形成的样品程序升温还原图谱和红外光谱均有所差别,H₂/N₂气氛下合成的样品有较好的磁性,而氩气和空气下合成的样品的磁性几乎为零。对于H₂/N₂气氛下合成的单相Sr₂FeMoO₆样品的甲烷催化燃烧活性测试表明,甲烷燃烧起燃温度T₁₀为475℃,完全转换温度T₁₀₀为744℃,可见单相双层钙钛矿型结构化合物Sr₂FeMoO₆对甲烷催化燃烧也有很好的活性。     

甲烷空气部分氧化制合成气喷动床反应器的研究

On the basis of hydrodynamic and scaling-up studies, a pilot-plant-scale thermal spouted bed reactor (50 mm in ID and 1500 mm in height) was designed and fabricated by scaling-down cold simulators. It was tested for making syngas via catalytic partial oxidation (CPO) of methane by air. The effects of various operating conditions such as operating pressure and temperature, feed composition, and gas flowrate etc. on the CPO process were investigated. CH4 conversion of 92.20％ and selectivity of 92.3% and 83.30/0 to CO and H2, respectively, were achieved at the pressure of 2.1 MPa. It was found that when the spouted bed reactor was operated within the stable spouting flow regime, the temperature profiles along the bed axis were much more uniform than those operated within the fixed-bed regime. The CH4 conversion and syngas selectivity were found to be close to thermodynamic equilibrium limits. The results of the present investigation showed that spouted bed could be considered as a potential type of chemical reactor for the CPO process of methane.     

Enhanced model predictive control of a catalytic flow reversal reactor

The combustion of lean methane air mixtures in a catalytic flow reversal reactor (CFRR) is studied using a two dimensional heterogeneous continuum model, based on mole and energy balance equations for the solid (the inert and catalytic sections of the reactor) and the fluid phases. Following a design of experiments (DOE), many simulations were carried out to investigate the reactor performance. The results show the impact on the methane conversion and the maximum temperature in the reactor of key process parameters such as the methane inlet concentration, the superficial gas velocity, the switching time, and the mass extraction rate. A simple empirical model is deduced to predict the maximum temperature and conversion of methane in the reactor at stationary state. This model is combined with a model predictive control (MPC) strategy in the form of a terminal constraint to improve the controller performance. Results show that the control of the reactor is improved.     

Demonstration of a control system for combustion of lean hydrocarbon emissions in a reverse flow reactor

In this work, the performance of a simple logic-based controller for a reverse flow reactor (RFR) has been tested experimentally. The controller is a hybrid system using the inside reactor temperature as the controlled variable, and the switch of the flow direction as the manipulated variable. Three different control logic rules (depending on the point selected to measure the inside reactor temperature) have been compared for the catalytic combustion of methane in a bench-scale RFR unit. A procedure for tuning the controllers was established. The controller that measures the temperature in the middle of the reactor showed the best performance, as it provided complete methane conversion with high capacity to overcome both low and high feed concentration disturbances.