CN106391036A - 一种乙酸自热重整制氢的固溶体催化剂及制备方法 - Google Patents
一种乙酸自热重整制氢的固溶体催化剂及制备方法 Download PDFInfo
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Abstract
本发明涉及一种乙酸自热重整制取氢气的镍基固溶体催化剂。针对现有催化剂在乙酸自热重整反应中催化剂活性组分的氧化、烧结和积炭等因素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、活性稳定的新的催化剂，其重量组成是(NiO)a(YO1.5)b(ZrO2)c，其中a为0.07‑0.20，b为0.02‑0.35，c为0.58‑0.91。本发明催化剂采用氧化锆为载体，并引入助剂氧化钇，以聚环氧乙烷‑聚环氧丙烷‑聚环氧乙烷三嵌段共聚物作为模板剂，经蒸发自组装形成了介孔结构，获得稳定的以ZrxY1‑xOy固溶体为主体结构的镍基催化剂，有效提高了乙酸自热重整过程氢气产率、稳定性和抗积炭能力。
Description
技术领域
本发明涉及一种乙酸自热重整制取氢气的镍基固溶体催化剂及其制备方法，属于乙酸自热重整制氢的领域。
背景技术
人类社会在高速发展的同时，对能源的需求也在不断的加大，寻找传统化石燃料的替代资源已经成了当今世界的迫切目标。氢气具有热值高的特点，而其燃烧产物是水，对环境无污染，可作为一种清洁替代能源。氢气的传统来源一般为煤炭、天然气等化石资源，而生物质由于其可再生而且相对廉价，因此生物质制氢已成为当今世界备受关注的生物质利用技术之一。不过，由于生物质能量密度低，存储和输送不便，因此研究者用快速热解的方式将生物质转化为方便储运的生物质油。生物质油成分复杂，研究者往往选择生物质油的典型组分乙酸作为模型化合物，探索催化重整制取氢气的高效转化途径。
乙酸催化转化制取氢气，常用的方法是水蒸气重整制氢。该方法由于水蒸气本身也会参与反应，因此可以获得较高浓度的氢气。但是水蒸气重整反应是一个吸热反应，需要持续供应热能，才能维持反应的进行。而且，在水蒸气重整制氢反应中，乙酸转化的副产物容易在催化剂上形成积碳，从而降低催化剂的活性。
自热重整过程是将吸热的蒸汽重整与放热的部分氧化重整相结合，因其整合了吸热与放热反应，可以通过控制原料气里氧气的量来实现反应热量平衡，从而不需要外界供热。因此，自热重整结构更为简单，不需要大型的换热装置，同时对制氢原料也有更高的适应性，适合于含乙酸的生物质油等复杂组分的催化转化过程。
现阶段用于乙酸催化转化过程的催化剂主要有贵金属催化剂和非贵金属催化剂。贵金属催化剂主要包括Pd、Ru、Rh、Pt等催化剂，具有活性高、抗积炭等特点。不过，贵金属催化剂价格昂贵，而限制了其应用。Ni、Co等非贵金属催化剂的成本相对较低，尤其是Ni基催化剂，在烃类催化重整过程等传统化工过程中具有较高的C-C裂解活性，目前已成为乙酸制氢的重点研究催化剂之一。
Ni基催化剂在乙酸自热重整反应中，能有效促进乙酸分子中碳碳键的断裂，使得反应产物中气体产物所占百分比增大，而副产物产物如丙酮、乙烯酮等的百分比减小，从而获得较高的乙酸的转化率和H2的产率。不过，通常采用的氧化铝担载镍基催化剂，在选择性方面，产品气中CH4含量偏高，而且由于Ni对含碳物种的裂解性能和载体氧化铝的强酸性，常伴有明显的积碳问题。同时，由于自热重整过程中引入了氧气，氧气主要消耗在催化剂床层反应前端，导致反应前端的温度升高，最高可达1000摄氏度以上，从而导致床层反应前端催化剂的烧结、氧化而失活，使得反应前端不断后移，最终导致整个催化剂床层失活。因此，提高Ni基催化剂的热稳定性、抗氧化性、抗积炭性，并降低对CH4等副产物的选择性，是获得高活性、高稳定性催化剂的关键所在。
在Ni基催化体系中，载体和助剂的选择和组合因此成为优化催化剂的重要因素。在载体选择方面，ZrO2具有适中的酸性和碱性，较高的供电子能力，同时也具有较高的热稳定性，可有效促进活性组分Ni对乙酸的分解并抑制Ni金属的氧化，利于制氢反应的进行。在助剂选择方面，过渡金属氧化物Y2O3本身具有较强碱性，而且可以有效提高催化剂的比表面积。更重要的是，载体ZrO2和助剂Y2O3可形成固溶体，而活性组分Ni则可高度分散在固溶体中，抑制Ni晶体的聚集长大，从而有效提高催化剂的耐烧结稳定性。
催化剂的制备方法也是获得高效催化剂的一个重要手段。相比共沉淀法等常规制备手段，蒸发自组装的制备方法采用了等温条件下，在不同pH值及浓度条件下，将催化剂前驱体溶液进行等温蒸发自组装，能够有效提高催化剂的比表面积，并构建出有序介孔结构，从催化反应动力学方面控制并促进反应物分子的扩散过程，抑制副产物的生成和脱附，从而有效提高反应的选择性和抗积炭能力。本发明采用蒸发自组装法来制备催化剂，使用聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物(P123)作为模板剂，构建出了Ni-Y-Zr-O固溶体的有序介孔材料，应用于乙酸自热重整过程，获得了活性高、稳定性好、耐积炭、耐氧化的镍基固溶体催化材料。
发明内容
本发明所要解决的技术问题是，针对现有镍基催化剂在乙酸自热重整反应中积炭和活性组分的氧化及烧结，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、活性稳定的新的催化剂。
本发明以镍为活性组分，以ZrO2为载体，引入Y2O3作为助剂，并采用蒸发自组装方法，获得稳定的以ZrxY1-xOy固溶体为主体结构的Ni-Zr-Y-O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，乙酸转化率接近100％，氢气产率可稳定在3.05mol-H2/mol-AC。
本发明技术方案：
本发明针对乙酸自热重整的特点，以蒸发自组装法制备了Ni-ZrO2催化剂，同时添加不同含量的Y2O3作为助剂，经焙烧后形成了以ZrxY1-xOy固溶体为主体结构的Ni-Zr-Y-O催化剂，有效提高了催化剂的比表面积，并构建出有序介孔结构，促进反应物分子的扩散过程，抑制了副产物的生成和脱附，有效提高了乙酸自热重整的活性和稳定性。本发明的催化剂的重量组成是(NiO)a(YO1.5)b(ZrO2)c，其中a为0.07-0.20，b为0.02-0.35，c为0.58-0.91，即按照重量百分比组成为：氧化镍为7.0-20.0％，氧化钇为2.0-35.0％，氧化锆为58.0-91.0％。本发明优选的催化剂的重量百分比为：氧化镍为9.8％，氧化钇为19.8％，氧化锆为70.4％。
具体制备方法包括以下步骤：
1)配制溶液：称取一定量的聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物(P123)，加入无水乙醇中，常温搅拌1h，得到一定浓度的溶液；准确称取一定量的硝酸镍、硝酸氧锆、硝酸钇等，加入到前述溶液中，继续常温搅拌5h；
2)将步骤1)溶液转移到结晶皿中，放入烘箱中保持60℃直至样品干燥；
3)将步骤2)的样品放入焙烧炉中，在650-850℃的温度下焙烧4h，焙烧完成后冷却到室温，得到具有Ni-Zr-Y-O结构的固溶体催化剂，其XRD图谱如附图1所示；
4)将步骤3所得催化剂(50-300mg)于500-850℃的温度下在H2中还原1h活化处理，经氮气吹扫，通入摩尔比为乙酸/水/氧气＝1/(1.3-5.0)/(0.21-0.35)的混合气体，通过催化剂床层进行自热重整反应，反应温度为500℃-850℃。
本发明的有益效果：
1)本发明催化剂以镍为活性组分，以ZrO2为载体，，并引入助剂Y2O3，形成了稳定的ZrxY1-xOy固溶体，而活性组分Ni则高度分散在固溶体中，获得了如附图1所示的Ni-Zr-Y-O固溶体催化剂，有效抑制了Ni晶体的聚集长大，而ZrO2适中的酸性和碱性以及较高的供电子能力，有效促进了活性组分Ni对乙酸的分解并抑制Ni金属的氧化，从而有效提高了催化剂的活性组分分散度、热稳定性和耐氧化能力。
2)本发明催化剂制备中采用聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物(P123)作为模板剂，经蒸发自组装形成了有序介孔结构的Ni-Zr-Y-O固溶体，有效提高了催化剂的比表面积，促进了反应物分子的扩散过程，抑制了丙酮、乙烯酮等大分子副产物的生成，从而有效提高反应的选择性和抗积炭能力。
3)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、活性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X射线衍射谱图
具体实施方式
参照例1
称取1.0000g的聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物(P123)，加入到20ml无水乙醇中，覆盖保鲜膜后常温磁力搅拌1h，得到溶液#1。称取0.4362g的Ni(NO3)·6H2O和2.1718g的ZrO(NO3)·2H2O，加入到溶液#1，继续常温搅拌5h后，转移到结晶皿中，在烘箱中恒温60℃蒸发至样品干燥，然后将蒸干的样品于700℃焙烧4h，冷却到室温，得到催化剂CUT-NZ，该催化剂的重量百分比组成为：氧化镍含量为9.7％，氧化锆含量为90.3％。
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，然后筛分成10-20目颗粒，装入反应器中，在500-850℃的温度下在H2中还原1h后，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，形成摩尔比为乙酸/水/氧气＝1/(1.3-5.0)/(0.21-0.35)的反应原料气，并将此原料气导入反应床层，反应条件为常压、空速8000-40000mL/(g-catalyst.h)、反应温度500℃-850℃，通过催化剂床层进行反应；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。
该催化剂CUT-NZ经乙酸自热重整活性考察，反应条件为常压、空速30000mL/(g-catalyst.h)、反应温度700℃、原料气乙酸/水/氧气＝1/4.0/0.28时，该催化剂的初始乙酸转化率为95.3％，氢气产率为2.98mol-H2/mol-AC，但是随着反应的进行，由于烧结、积炭、氧化等原因，出现了丙酮、乙烯酮等副产物，反应活性下降，反应时间10h后，乙酸转化率降低到84.2％，氢气产率降低到2.48mol-H2/mol-AC。
实施例1
称取1.0000g的P123，加入到20ml无水乙醇中，覆盖保鲜膜后常温磁力搅拌1h，得到溶液#1。称取0.4362g的Ni(NO3)2·6H2O、2.0045g的ZrO(NO3)2·2H2O和0.3830g的Y(NO3)3·6H2O，加入到溶液#1，继续常温搅拌5h，后续步骤同参照例1，得到具有如附图1所示固溶体结构的催化剂CUT-NZY10。该催化剂的重量百分比组成为：氧化镍为9.7％，氧化锆为80.5％，氧化钇为9.8％。
该催化剂CUT-NZY10经乙酸自热重整活性考察，反应条件为常压、空速30000mL/(g-catalyst.h)、反应温度700℃、原料气乙酸/水/氧气＝1/4.0/0.28时，该催化剂乙酸转化率稳定在100％，氢气产率初始为3.05mol-H2/mol-AC，随着反应的进行，氢气产率小幅降低到2.95mol-H2/mol-AC并且维持稳定。对反应后催化剂进行了XRD、XPS、SEM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，同时无明显积炭。
实施例2
称取1.0000g的P123，加入到20ml无水乙醇中，覆盖保鲜膜后常温磁力搅拌1h，得到溶液#1。称取0.4362g的Ni(NO3)2·6H2O、1.7373g的ZrO(NO3)2·2H2O和0.7661g的Y(NO3)3·6H2O，加入到溶液#1，继续常温搅拌5h，后续步骤同参照例1，得到具有如附图1所示固溶体结构的催化剂CUT-NZY20。该催化剂的重量百分比组成为：氧化镍为9.8％，氧化锆为70.4％，氧化钇为19.8％。
该催化剂CUT-NZY20经乙酸自热重整活性考察，在空速为30000mL/(gcatalyst·h)，反应温度为700℃，进料比为AC/H2O/O2/N2＝1/4/0.28/4.2的条件下，该催化剂的乙酸转化率为100％，氢气的产率为3.05mol-H2/mol-AC，并在10h的测试中保持稳定。对反应后催化剂进行了XRD、XPS、SEM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，同时无明显积炭。
由活性测试结果可见，本发明的催化剂在乙酸自热重整反应中，乙酸转化率达到100％，优化催化剂的氢气产率达到3.05molH2/molAC，并保持稳定；通过XRD、XPS、SEM等表征表明，本催化剂具有结构稳定、耐烧结、抗积炭、耐氧化等特点。
Claims (4)
1.用于乙酸自热重整制氢的镍基固溶体催化剂，其特征在于：配制聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物(P123)的无水乙醇溶液，加入硝酸镍、硝酸氧锆、硝酸钇等硝酸盐，常温搅拌5h后，将溶液转移到结晶皿中，于60℃恒温蒸干，在650-850℃的温度下焙烧4h，得到具有Ni-Zr-Y-O固溶体结构的催化剂，其重量组成是(NiO)a(YO1.5)b(ZrO2)c，其中a为0.07-0.20，b为0.02-0.35，c为0.58-0.91，即按照重量百分比组成为：氧化镍为7.0-20.0％，氧化钇为2.0-35.0％，氧化锆为58.0-91.0％；该催化剂用于乙酸自热重整制氢过程。
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：氧化镍为9.7％，氧化锆为80.5％，氧化钇为9.8％。
3.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：氧化镍为9.8％，氧化锆为70.4％，氧化钇为19.8％。
4.权利要求1-3所述催化剂在乙酸自热重整制氢反应的用途，其特征在于：将50-300mg权利要求1-3任一项所述催化剂于500-850℃在H2中还原1h后，通入摩尔比为乙酸/水/氧气＝1/(1.3-5.0)/(0.21-0.35)的混合气体，通过催化剂床层进行乙酸自热重整反应，反应温度为500-850℃。
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