CN107042111A - 一种乙酸自热重整制氢的层状钙钛矿型催化剂及制备方法 - Google Patents
一种乙酸自热重整制氢的层状钙钛矿型催化剂及制备方法 Download PDFInfo
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Abstract
本发明涉及一种乙酸自热重整制氢的层状钙钛矿型催化剂及制备方法。本发明针对现有催化剂在乙酸自热重整过程中烧结、氧化、积炭并导致催化剂失活的问题,提供一种耐烧结、抗积炭、耐氧化、活性高的新的催化剂。本发明以溶胶凝胶法制备了A2BO4型层状钙钛矿结构的镍基催化剂,化学成分是La2‑xCaxNiO4,其中x=0‑1.5;通过以钙部分取代镧,增加了钙钛矿催化剂表面的氧缺陷和晶格结构缺陷,提高了活性组分镍的还原性、热稳定性和抗氧化性,从而提高了催化剂的活性和稳定性。
Description
技术领域
本发明涉及一种乙酸自热重整制氢的层状钙钛矿型镍基催化剂及其制备方法,属于乙酸自热重整的制取氢气的领域。
背景技术
人类社会经济在高速发展的同时,对能源的需求不断加大,寻找传统化石燃料的替代能源已经成了当今世界的迫切目标。氢气是一种重要的化工原料,也是一种清洁能源,并可用于燃料电池,被视为未来的清洁能源载体。目前,主流的氢气制取来自于煤炭、天然气等化石资源的转化,带来了环境污染问题。要实现对氢能的高效长期利用,需要解决的首要问题就是找到清洁的、廉价易得的氢源。
生物质具有资源丰富、可再生等优点,而生物质制氢过程是一个碳中性的规模化获取氢能源的有效途径。生物质能量密度低,可以高温下裂解制取生物质油,再集中后经由水蒸气重整规模化制取氢气。
在生物质油中,乙酸作为其主要的液相组成成分,质量分数可达30%,因此,可经催化重整过程获得氢气。在现阶段,对乙酸的蒸汽重整制氢过程研究较多;不过,蒸汽重整过程是吸热反应,需要换热器供给反应热,以维持反应的进行。乙酸自热重整,是一种具有较好前景的过程;该过程以乙酸、水和氧气或者空气为原料制取氢气,结合了蒸汽重整和部分氧化反应,通过调节原料气中氧气和乙酸的比例,可以平衡反应热;同时,氧气的加入,通过氧化含碳物种,抑制积炭前驱体的形成,从而可以缓解催化剂可能的积炭。
乙酸自热重整反应的特点是在原料气中加入了氧气,而氧气主要在催化剂床层的反应前端反应,使得反应前端局部温度可高达1000摄氏度,导致催化剂的烧结和活性组分聚集变大,从而导致活性中心数的减少;而氧气的存在,在反应前端的活性组分容易被氧化。这两个因素,容易导致催化剂的失活。同时,乙酸分子在催化剂表面活化后,在自热重整过程中会经脱羧反应和脱水反应,生成乙烯酮等中间物种,发生缩聚反应形成积炭,沉积在催化剂表面,隔离催化剂和反应物,导致催化剂活性下降。因此,开发结构稳定、耐氧化及耐烧结和抗积炭的催化剂是自热重整反应制取氢气的需要解决的关键问题。
镍金属由于活性高、易得而常应用于加氢和脱氢反应。在乙酸催化转化过程中,镍能促进乙酸碳碳键断裂,有利于提高气态产物含量,提高氢气收率和选择性。此外,活性金属镍对水气变换反应和甲烷重整反应具有较高的催化活性,可以促使产物中的一氧化碳和甲烷转变为氢气和二氧化碳。因此,与常用的Pt、Au、Rh等贵金属催化剂相比,Ni基催化剂也是一个较好的选择。然而,镍基催化剂在乙酸自热重整过程中,也面临着烧结、积炭等问题。
为了能够较好解决镍基催化剂活性组分聚集烧结和积碳等问题,将活性组分镍负载在氧化物载体上,有利于活性组分镍的分散和粒子的稳定。本发明镍基催化剂选择了氧化镧和氧化钙作为载体:氧化镧具有较好的热稳定性,并有较强的活化水分子和二氧化碳的能力,与二氧化碳反应生成La2O2CO3后(La2O3+CO2→La2O2CO3),在自热重整过程中与积炭前驱体通过La2O2CO3+*C→La2O3+2CO+*反应(其中*为催化剂活性位),氧化转化积碳前驱体为气态产物,有效地抑制积碳。另一方面,氧化钙热稳定性好,并有很强的吸附二氧化碳的能力,也有利于CO2氧化转化积炭前驱物;同时,可与氧化镧形成La-Ca-O复合氧化物,提高催化剂的比表面积,从而提高催化活性。
考虑催化剂的结构问题,为应对烧结和氧化的问题,本发明催化剂采用Ca掺杂的A2BO4层状钙钛矿结构的镍基催化剂。A2BO4钙钛矿型催化剂热稳定性和化学稳定性较好,A位多采用La等稀土金属,B位多为Fe、Co、Ni等过渡金属,由于A和B一般可以部分被取代,从而增加钙钛矿型催化剂表面缺陷位和晶格缺陷结构,抑制催化剂活性组分的氧化;另外,A2BO4层状结构有利于反应物乙酸、水蒸气和氧气的扩散,同时抑制了积炭前驱物如乙烯酮等较大中间产物的形成,从而抑制积炭,并提高了氢气的选择性,提高了催化活性和稳定性。
本发明采用溶胶凝胶法制备层状钙钛矿结构的镍基催化剂,在制备过程中经水解、缩合反应,在溶液中形成稳定的透明溶胶体系,溶胶经陈化,胶粒间缓慢聚合,形成三维网络结构的凝胶,经焙烧后,可以得到产物成分分布均匀的复合金属氧化物。
发明内容
本发明所要解决的技术问题是,针对现有催化剂在乙酸自热重整反应中催化剂结构的变化和活性组分的氧化及烧结,从而导致催化剂的失活的问题,提供一种结构稳定、耐烧结、抗积炭、耐氧化、稳定的新的催化剂。
本发明用镍作为活性组分,La2O3为载体,引入助剂Ca后,形成层状钙钛矿结构的La2-xCaxNiO4催化剂。将本发明催化剂用于乙酸自热重整制氢反应中,在反应温度为700℃的情况下,乙酸转化率可到达100%,氢气产率稳定在2.82mol-H2/mol-AC。
本发明的技术方案:
本发明针对乙酸自热重整的特点,以溶胶凝胶法制备了具有层状钙钛矿型结构的La2-xCaxNiO4催化剂,引入了碱性金属Ca作为助剂,部分替代La,增加该层状钙钛矿型催化剂表面缺陷位,还原性能提高,同时有效的提高了催化剂的稳定性。本发明的催化剂的化学成分是La2-xCaxNiO4,其中x=0-1.5。
本发明优选的催化剂为LaCaNiO4;该催化剂组成以氧化物的重量百分比计为:氧化镧为55.5%,氧化镍为25.4%,助剂氧化钙为19.1%。
本发明催化剂的具体的制备方法的步骤如下:
1)配制金属盐的混合溶液:根据化学组成为La2-xCaxNiO,其中x=0-1.5,配制镧、镍及钙的硝酸盐的混合溶液;
2)配制柠檬酸溶液:按照金属阳离子La、Ni以及Ca的物质的量的总和与柠檬酸的摩尔比为1︰1的要求,配制柠檬酸溶液;
3)配制乙二醇溶液:按照柠檬酸和乙二醇的摩尔比为1:1的要求,配制乙二醇溶液;
4)将步骤1)配制的硝酸盐溶液和步骤3)配制的乙二醇溶液缓慢滴加到步骤2)配制的柠檬酸溶液中,并在70℃条件下搅拌,经4小时后,溶液逐渐转化为胶体,放入烘箱中,在105℃下干燥12小时;
5)将步骤4)所述的干燥后的样品,置入管式炉中,以10℃/min的速度升温至600-800℃,焙烧6小时,即得到本发明催化剂,其XRD谱图如附图1所示,其显示出典型层状钙钛矿型结构;本发明催化剂使用前于H2气氛中500-800℃还原1小时进行活化处理,经氮气吹扫,通入汽化后的乙酸/水/氧气的摩尔比为1.00/(1.00-4.00)/(0.21-0.35)/3.90的混合气体,通过催化剂床层进行反应,反应温度为500-800℃。
本发明的有益效果:
1)本发明以溶胶凝胶法制备了A2BO4型层状钙钛矿结构的镍基催化剂La2-xCaxNiO4(x=0-1.5),通过A位的Ca部分取代La,增加钙钛矿催化剂表面的氧缺陷和晶格结构缺陷,提高了催化剂的活性。
2)本发明催化剂采用氧化镧作为载体的主要成分,通过La2O3-La2O2CO3的催化循环,即通过La2O3+CO2→La2O2CO3和La2O2CO3+*C→La2O3+2CO+*(其中*为催化剂活性位)的催化循环,提高了CO2氧化积炭前驱物的能力,抗积炭能力增强。
3)本发明引入钙作为助剂,提高了活性组分镍的还原性;Ca为碱性助剂,减少了催化剂酸性位,能够有效的抑制了积炭;其热稳定性也较好,利于提高催化剂的稳定性。
4)本发明催化剂经乙酸自热重整反应结果表明,本发明的催化剂具有耐烧结、抗积炭、耐氧化、结构稳定并且氢气产率高等特点。
附图说明
附图1:本发明催化剂的XRD图
具体实施方式
参照例一
称取8.6494克的La(NO3)3·6H2O和2.9044克的Ni(NO3)2·6H2O,加入30ml的去离子水中,配制成溶液#1;然后称取6.2966克的柠檬酸C6H8O7·H2O,加入30ml的去离子水中,配制成溶液#2;再称取1.8599克的乙二醇(CH2OH)2;将溶液#1和乙二醇缓慢滴加到溶液#2中,并在70℃条件下搅拌4小时,溶液逐渐转化为胶体,并转入干燥箱在105℃下烘干12小时。将经干燥后的样品放入瓷舟中,置入管式炉中,以10℃/min的速度升温至700℃,保持700℃焙烧6小时,经扫描电子显微镜和X-射线衍射仪观察,得到具有层状钙钛矿型结构的催化剂CDUT-LN,其摩尔组成为La2NiO4,其典型的XRD谱图如附图1所示。该催化剂的重量组成为:氧化镧的含量为81.4%,氧化镍含量为18.6%。
乙酸自热重整反应活性评价在连续流动固定床反应器中进行。将催化剂研磨并压片,筛分成20-40目,装入反应器中,并在500-800℃的温度下,以20.0mL/min流量的H2中还原1h;将乙酸和水的混合溶液以注射泵注入汽化器经汽化后,混合氧气,并以氮气为内标气体,形成AC/H2O/O2/N2的摩尔比为1.00/(1.00-4.00)/(0.21-0.35)/3.90的混合气体,并将此原料气导入反应床层,反应条件为温度500-800℃、常压、空速5000-25000h-1,反应尾气以配置热导检测器和氢火焰离子化检测器以及填充柱(Porapaq-QS和5A)和毛细管柱(Q-Plot)的气相色谱仪分析。
催化剂CDUT-LN经乙酸自热重整反应活性考察,在温度700℃、空速7500h-1、AC/H2O/O2/N2=1.00/4.00/0.28/3.90时,该催化剂具有较高的初活性,乙酸转化率为100%,氢气产率为2.83mol-H2/mol-AC。但随着反应的进行,由于烧结、氧化等原因,反应活性迅速下降,二氧化碳和一氧化碳的选择性下降,而副产物如丙酮等出现并显著上升,导致氢气产率下降,在反应10小时后,氢气产率仅为2.25mol-H2/mol-AC,同时乙酸的转化率降低到84.7%。
实施例一
称取5.8979克的La(NO3)3·6H2O,,3.908克的Ni(NO3)2·6H2O和3.2165克的Ca(NO3)2·4H2O,加入30ml的去离子水中,配制成溶液#1。称取8.5863克的C6H8O7·H2O,加入30ml的去离子水中,配制成溶液#2。再称取2.5362克的(CH2OH)2。将溶液#1和乙二醇缓慢滴加到溶液#2中,并在70℃条件下搅拌4小时,溶液逐渐转化为胶体,并转入干燥箱在105℃下烘干12小时。将经干燥后的样品放入瓷舟中,置入管式炉中,以10℃/min的速度升温至700℃,保持700℃焙烧6小时,得到具有层状钙钛矿型结构的CDUT-LC10N催化剂,其摩尔组成为LaCaNiO4,其XRD谱图如附图1所示,其结果表明在加入助剂Ca后,仍然形成了层状钙钛矿结构。该催化剂的重量组成为:氧化镧的含量为55.5%,氧化镍含量为25.4%,氧化钙含量为19.1%。
催化剂CDUT-LC10N在乙酸自热重整反应中进行活性评价,在温度700℃、空速7500h-1、AC/H2O/O2/N2=1.00/4.00/0.28/3.90时,乙酸转化率稳定在100%,同时甲烷和丙酮等副产物受到抑制,氢气产率稳定在约2.82mol-H2/mol-AC,在10小时内没有观察到乙酸的转化率下降和氢气产率下降等失活现象。对反应后催化剂进行了XRD、XPS、SEM、TG等表征,结果表明,该催化剂的结构稳定、活性组分的价态稳定,无明显积炭。
实施例二
称取3.6045克的La(NO3)3·6H2O,,4.8414克的Ni(NO3)2·6H2O和5.8973克的Ca(NO3)2·4H2O,加入30ml的去离子水中,配制成溶液#1。称取10.4965克的C6H8O7·H2O,加入30ml的去离子水中,配制成溶液#2。再称取3.1004克的(CH2OH)2。将溶液#1和乙二醇缓慢滴加到溶液#2中,并在70℃条件下搅拌4小时,溶液逐渐转化为胶体,并转入干燥箱在105℃下烘干12小时。将经干燥后的样品放入瓷舟中,置入管式炉中,以70℃/min的速度升温至700℃,保持700℃焙烧6小时,得到具有层状钙钛矿型结构的CDUT-LC15N催化剂,其摩尔组成为La0.5Ca1.5NiO4,通过XRD测试,结果表明催化剂形成了层状钙钛矿结构,并伴随少量氧化钙物相生成。该催化剂的重量组成为:氧化镧的含量为33.9%,氧化镍含量为31.1%,氧化钙含量为35.0%。
催化剂CDUT-LC15N在乙酸自热重整反应中进行活性评价,在温度700℃、空速7500h-1、AC/H2O/O2/N2=1.00/4.00/0.28/3.90时,反应时间为10h内,其乙酸转化率稳定在100%,氢气产率稳定在约2.66mol-H2/mol-AC,同时丙酮等副产物得到抑制。对反应后催化剂进行了XRD、XPS、SEM、TG等表征,结果表明,该催化剂的结构稳定、活性组分的价态稳定,无明显积炭。
由活性测试结果可见,对比参照例1,本发明的实施例1和实施例2在乙酸自热重整制氢反应中,乙酸转化率达到100%,氢气产率分别达到2.82mol-H2/mol-AC和2.66mol-H2/mol-AC,并保持稳定。通过XRD、XPS、TG、SEM等表征表明,在引入助剂钙后,本发明催化剂具有活性稳定、耐烧结、抗积炭、耐氧化等特点。
Claims (5)
1.用于乙酸自热重整制取氢气的层状钙钛矿型镍基催化剂,其特征在于:配制硝酸镧、硝酸镍和硝酸钙的混合溶液#1;按照金属阳离子镧、镍以及钙的摩尔数的总和与柠檬酸的摩尔比为1:1的要求,配制柠檬酸溶液#2;按照柠檬酸和乙二醇的摩尔比为1:1的要求,配制乙二醇溶液#3;在70℃水浴中,将溶液#1和溶液#3缓慢滴加到溶液#2中,并持续搅拌获得胶体,将所得胶体于105摄氏度烘干12小时,并于600-800摄氏度焙烧6小时,即得以层状钙钛矿型结构为主体的镍基催化剂;其化学成分是La2-xCaxNiO4,其中x=0-1.5;该催化剂用于乙酸自热重整制取氢气的反应过程。
2.根据权利要求1所述的乙酸自热重整制氢的镍基催化剂,其特征在于:所述催化剂以氧化物的重量百分比组成为:氧化镧为33.9-81.4%,氧化镍为18.6-31.1%,氧化钙为0-35.0%。
3.根据权利要求2所述的乙酸自热重整制氢的镍基催化剂,其特征在于:所述催化剂以氧化物的重量百分比组成为:氧化镧为55.5%,氧化镍为25.4%,氧化钙为19.1%。
4.根据权利要求2所述的乙酸自热重整制氢的镍基催化剂,其特征在于:所述催化剂以氧化物的重量百分比组成为:氧化镧为33.9%,氧化镍为31.1%,氧化钙为35.0%。
5.权利要求1-4任一项所述催化剂在乙酸自热重整制氢反应的用途,其特征在于:取50-300mg权利要求1-4任一项所述催化剂在于500-800℃的温度下在H2中进行还原1h,经氮气吹扫,通入流量为50-250ml/min的乙酸/水/氧气的摩尔比为1.00/(1.00-4.00)/(0.21-0.35)的混合气体,通过催化剂床层进行反应,反应温度为500-800℃。
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