CN111229250B - 一种乙醇重整催化剂及其制备和应用 - Google Patents
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Abstract
本发明涉及一种用于乙醇重整的LaxSryNizTi1‑zO3钙钛矿催化剂的制法及应用,属于固体氧化物燃料电池和催化剂技术领域,其特征是,包括如下步骤:1)LaxSryNizTi1‑zO3钙钛矿催化剂的制备;2)用固定床反应器,该催化剂乙醇重整反应温度:400‑850℃;乙醇的转化率为80‑100%。该催化剂用于乙醇为燃料的固体氧化物燃料电池,具有良好的催化重整活性、抗积碳性能和抗高温烧结性能。
Description
技术领域
本发明涉及固体氧化物燃料电池,具体地说是一种用于固体氧化物燃料电池乙醇重整LaxSryNizTi1-zO3钙钛矿催化剂,通过高温烧结得到的LaxSryNizTi1-zO3钙钛矿催化剂,具有抗积碳性能好、活性高、高温稳定等特点,是一种十分符合固体氧化物燃料电池采用乙醇为燃料时的重整催化剂,这种高活性、高稳定性的乙醇重整催化剂在固体氧化物燃料电池系统方面具有重要的意义,对于推动固体氧化物燃料电池技术向应用技术的发展具有重要的意义。
背景技术
能源和环境已成为关系到人类社会可持续发展的两大热点问题。随着人类社会现代化进程的不断推进,对能源的依赖和化石能源日益枯竭的矛盾日益加剧。能源生产和使用过程中排放大量污染物和CO2等温室气体,是重要空气污染源的原因之一。寻找一种清洁、高效和CO2净排放低的能源技术已成为人类社会发展之迫切需要。
固体氧化物燃料电池是将化学能直接转化为电能的能量转换装置,采用全固态结构,具有发电效率高、可直接采用碳氢化合物为燃料、应用范围广等特点,是理想的分散发电和集中电站技术,也可以应用于车辆辅助电源、便携式电源等。乙醇来源广泛,不会过渡消耗化石资源。从长远的观点考虑,生物发酵法制乙醇必将再度成为主流,生物质乙醇可以通过生物质或食品、畜牧业的废弃物发酵生成。乙醇制氢释放出来的CO2又通过光合作用转变为生物质,形成一个碳的闭合循环,实现了C02的零排放,减少了大气污染和温室效应,所以乙醇是可再生的洁净能源。乙醇无毒,常温常压下呈液态,更容易运输和携带,操作方便,搬运灵活,使用方便,在自然界中也更易于被生物降解。乙醇的比能量远远高于甲醇和氢气。因此,如何开发出具有高活性、高选择性的乙醇水蒸气重整催化剂对于燃料电池的发展具有重要意义。与天然气、汽油、甲醇等重整原料相比,乙醇重整具有环境友好和氢气收率高等特点,乙醇重整反应包括:
A.乙醇水蒸气重整CH3CH2OH+3H2O→6H2+2CO2
B.乙醇水蒸气重整CH3CH2OH+H2O→4H2+2CO
C.水气转化反应CO+H2O→H2+CO2
乙醇水蒸汽重整反应是一个强吸热反应,而固体氧化物燃料电池的放电过程和尾气燃烧过程为放热过程,高效的固体氧化物燃料电池发电系统需要将这些过程耦合起来,乙醇重整反应要耦合吸收固体氧化物燃料电池的余热,则需要重整催化剂适应较为宽泛的温度范围并且具有很好的稳定性,通常也需要400-850℃反应温度;要求催化剂既能在较低的温度下进行,又要在较高的温度下具有较好的抗烧结性能。如何在高低温下都能具有较高的活性和稳定性,在这样的背景下,构建和制备该催化剂。
发明内容
本发明的目的是提供一种适用于固体氧化物燃料电池乙醇重整LaxSryNizTi1-zO3钙钛矿催化剂及其制法。
本发明具体采用的技术方案是:
一种用于固体氧化物燃料电池乙醇重整LaxSryNizTi1-zO3钙钛矿催化剂的制法,其特征是,采用固相法制备钙钛矿催化剂LaxSryNizTi1-zO3,其中,0≤x≤0.9,0≤y≤0.9,0.01≤z≤0.3包括如下步骤:
1)按金属离子摩尔比分别称取La2O3、SrO、NiO、TiO2,混合,球磨8-48小时;
2)置于高温炉中,于空气氛围下800-1400℃焙烧4-20h,得本发明的催化剂。
其中,步骤1)球磨8-48小时。
其中,步骤2)置于高温炉中,于空气氛围下800-1400℃焙烧4-20h。
一种用于固体氧化物燃料电池的乙醇重整LaxSryNizTi1-zO3钙钛矿催化剂,其中,0≤x≤0.9,0≤y≤0.9,0.01≤z≤0.3,其中0.1≤x≤0.8,0.1≤y≤0.8,0.02≤z≤0.25较好,0.2≤x≤0.7,0.2≤y≤0.7,0.05≤z≤0.2最好。
一种乙醇重整LaxSryNizTi1-zO3钙钛矿催化剂用于固体氧化物燃料电池的乙醇重整反应,在固定床反应器,反应温度:400-850℃。
本发明制备的催化剂,用于固体氧化物燃料电池的乙醇重整,具有抗积碳性能好、活性高、高温稳定等特点,能够在高低温下都能具有较高的活性和稳定性,是一种十分符合固体氧化物燃料电池采用乙醇为燃料时的重整催化剂。
具体实施方式
实施例1
1)LaxSryNizTi1-zO3钙钛矿催化剂的制备:按金属离子摩尔比为0.2:0.8:0.05:0.95的比例分别称取称取La2O3、SrO、NiO、TiO2,混合,球磨10小时;2)置于高温炉中,于空气氛围下1350℃焙烧4h。
2)催化剂应用和工艺条件:称取1g La0.2Sr0.8Ni0.05Ti0.95O3钙钛矿催化剂。乙醇和水的摩尔比为1:2的比例进行重整反应,汽化器温度150℃,反应温度800℃,N2作载气,乙醇流速0.1ml/min。乙醇的转化率为99%。
实施例2
1)LaxSryNizTi1-zO3钙钛矿催化剂的制备:按金属离子摩尔比为0.8:0.2:0.25:0.75的比例分别称取称取La2O3、SrO、NiO、TiO2,混合,球磨40小时;2)置于高温炉中,于空气氛围下1050℃焙烧15h。
2)催化剂应用和工艺条件:称取1gLa0.8Sr0.2Ni0.25Ti0.75O3钙钛矿催化剂。乙醇和水的摩尔比为1:3的比例进行重整反应,汽化器温度150℃,反应温度500℃,N2作载气,乙醇流速0.1ml/min。乙醇的转化率为90%。
实施例3
1)LaxSryNizTi1-zO3钙钛矿催化剂的制备:按金属离子摩尔比为0.4:0.6:0.1:0.9的比例分别称取称取La2O3、SrO、NiO、TiO2,混合,球磨25小时;2)置于高温炉中,于空气氛围下1250℃焙烧10h。
2)催化剂应用和工艺条件:称取1gLa0.4Sr0.6Ni0.1Ti0.9O3钙钛矿催化剂。乙醇和水的摩尔比为1:4的比例进行重整反应,汽化器温度150℃,反应温度700℃,N2作载气,乙醇流速0.1ml/min。乙醇的转化率为95%。
实施例4
1)LaxSryNizTi1-zO3钙钛矿催化剂的制备:按金属离子摩尔比为0.4:0.5:0.15:0.85的比例分别称取称取La2O3、SrO、NiO、TiO2,混合,球磨25小时;2)置于高温炉中,于空气氛围下1200℃焙烧15h。
2)催化剂应用和工艺条件:称取1gLa0.4Sr0.5Ni0.15Ti0.85O3钙钛矿催化剂。乙醇和水的摩尔比为1:3的比例进行重整反应,汽化器温度150℃,反应温度750℃,N2作载气,乙醇流速0.1ml/min。乙醇的转化率为96%。
Claims (5)
1.一种乙醇重整催化剂在固体氧化物燃料电池的乙醇重整反应中的应用,其特征是,所述催化剂为LaxSryNizTi1-zO3钙钛矿催化剂,其中,0.1≤x≤0.4,0.5≤y≤0.8,0.02≤z≤0.25,
采用固相法制备钙钛矿催化剂LaxSryNizTi1-zO3,包括如下步骤:
1) 按金属离子摩尔比分别称取La2O3、SrO、NiO、TiO2,混合,球磨8-48小时;
2) 置于高温炉中,于空气氛围下800-1400℃焙烧4-20h,得本发明的催化剂。
2.根据权利要求1所述的应用,其特征是,步骤1) 球磨12-36小时。
3.根据权利要求1所述的应用,其特征是,步骤2) 置于高温炉中,于空气氛围下1000-1300℃焙烧6-14h。
4. 根据权利要求1所述的应用,其特征是,钙钛矿催化剂LaxSryNizTi1-zO3,其中, 0.2≤x≤0.4,0.2≤y≤0.7,0.05≤z≤0.2。
5.根据权利要求1所述的应用,其特征是,在固定床反应器,反应温度:400-850℃。
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