CN1498682A - 一种加氢反应催化剂——储氢合金及其制备 - Google Patents
一种加氢反应催化剂——储氢合金及其制备 Download PDFInfo
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Abstract
一种加氢反应催化剂——储氢合金,其特征在于:在CaCu5型六方结构储氢合金材料LaNi5的基础上,添加微量合金元素以改善其催化性能,化学式为MlNiaCobMncAld,其中M1为富La的混合稀土;2.10≤a≤4.20.0.30≤b≤0.45,0.20≤c≤0.45,0.30≤d≤2.0;a+b+c+d=5。本发明中储氢合金催化剂具有高效、经济、安全的特点。本发明可以很好地促进有机化合物的加氢过程,如在烯烃、芳烃、炔烃、醛、酮、硝基化合物的加氢过程中可以获得较高的收率。
Description
技术领域:
本发明涉及一种新型的加氢反应催化剂——储氢合金及其制备技术,为储氢合金作为加氢反应催化剂提供了一条可行的实用化途径。
背景技术:
储氢合金是伴随着氢能和环境保护在最近二三十年才发展起来的新型多功能材料,在适当的温度、压力下具有大量可逆地吸收、释放氢的性能。储氢合金作为一种高效储能材料,具有如下特性:高储能密度、吸放氢反应伴随显著的热效应、选择性吸氢、电化学吸放氢及电催化活性、同位素分离效应及平台压力随温度呈指数变化等,这些特性的多样性决定了储氢合金应用的广泛性,如在镍—金属氢化物电池、在燃料电池、在能量转换技术中的应用得到广泛的研究和发展。储氢合金在中等温度和压力条件下即可快速、可逆地吸放大量氢气,反应时氢是以单原子存在于合金表面的(至少短时间内是这样的)。这就说明储氢合金在拆散H-H键方面有较强的能力,它们的表面具有相当大的活性。因此,储氢合金已成为多种加氢反应催化剂的研究对象。目前已研究的储氢合金作为催化剂的应用主要有下列几方面:1.烯烃、有机化合物的氢化反应;2.一氧化碳、二氧化碳的氢化反应;3.氨合成;4.氢化分解反应;5.异构化反应等。有关用储氢合金作为催化剂的催化机理,目前尚未建立起成熟的理论。但大量研究结果表明,未经预处理的储氢合金,没有或仅具有较低的活性,只有经过适当预处理改变表面活性中心的电子状态,增加活性中心数目,才能表现出高的活性。多数研究者认为Ni是储氢合金表面上使氢分子活化的中心,表面富Ni层是起催化作用的主要原因。另外在加氢反应中有些金属间化合物比传统催化剂具有更高的催化活性,但它们的比表面积却比传统催化剂的小许多,这一因素阻碍了金属氢化物作为催化剂的应用。所以增加金属氢化物的比表面积、增加表面活性中心数目对推动金属氢化物在催化剂方面的应用具有重要作用。
技术内容:
本发明的目的是提供一种用作加氢反应的储氢合金催化剂,及其制备和后续处理方法,以替代有机化合物的加氢过程中的传统催化剂,如在烯烃、芳烃、炔烃、醛、酮、硝基化合物的加氢过程中可以获得较高的收率。与传统催化剂如贵金属Pt、Pd和雷诺镍相比较,它具有高效、经济、安全的特点。
本发明提供的新型加氢反应催化剂——储氢合金,其特征在于:在CaCu5型六方结构储氢合金材料LaNi5的基础上,添加微量合金元素以改善其催化性能,化学式为MlNiaCobMncAld,其中Ml为富La的混合稀土;2.10≤a≤4.20,0.30≤b≤0.45,0.20≤c≤0.45,0.30≤d≤2.0;a+b+c+d=5。
本发明还提供了上述新型加氢反应催化剂——储氢合金的制备方法,其特征在于:母合金锭用真空感应熔炼制备,采用熔体旋转快淬法制成短条带或薄片,冷却方式为单辊快淬,辊轮线速度为10-35m/s,冷却速度为104-106℃/s,所得条带或薄片厚度为20-80μm,宽度为1-6mm。采用熔体旋转快淬法制备的储氢合金具有成分均匀、晶粒细小等优点。晶粒越细小,合金中晶界所占的比例就越大,由于晶界为氢扩散的通道,故晶粒细小的合金中氢扩散的通道数多,宏观表现在吸放氢速度快。
本发明同时提供了上述新型加氢反应催化剂——储氢合金的后续处理方法,其特点在于:在氩气保护下球磨成200目左右的粉,并采用KBH4碱溶液对其进行活化处理,活化过程分两步进行。第一步:取0.1-0.5gKBH4加入100ml 5-10%(mol)KOH溶液中配成KBH4碱溶液,再将一定量的储氢合金粉末置于该溶液中,然后在水浴中加热并搅拌均匀后,在50-100℃下保温1-3小时。第二步:向处理液中再加入0.8-2.6g的KBH4,然后在50-100℃下保温2-4小时。用KBH4碱溶液对储氢合金粉末进行处理,对其活性有明显影响。一方面是由于KOH溶解了铝锰等元素,使催化剂表面积增加;另一方面是由于氧化态的镍、钴被KBH4还原,在表面形成富镍层。
附图说明:
图1.反应过程中系统的压力随反应时间变化;
图2.反应产物的气相色谱谱图
具体实施方式:
实施例1
按合金设计的质量比[MlNi4.1Co0.3Mn0.2Al0.4]准确称取各组元纯金属(纯度均在99.0%以上),采用25kg真空感应炉熔炼,在氩气保护下浇铸。将铸锭用单辊快淬设备重熔快淬,辊轮线速度为35m/s,将快淬态合金在氩气保护下用机械方法粉碎至小于200目。取一定量的储氢合金粉末,采用KBH4碱溶液按权利要求3所述步骤进行活化后进行苯加氢反应。将苯置于间歇式高压反应釜中,将活化处理后的储氢合金粉洗涤后置入反应釜中,用氢气置换后加热升温。当升至预定温度后,通入一定压力的氢气进行苯加氢反应。反应一定的时间后取样,用气相色谱仪对其组成进行分析。图1为加氢过程中压力随时间的变化。从气相色谱对反应产物进行分析的结果(图2),可以看出苯的转化率及催化剂对环己烷的选择性均接近100%。
实施例2.
按合金设计的质量比[MlNi3.12Co0.36Mn0.32Al1.2]准确称取各组元纯金属(纯度均在99.0%以上),采用25kg真空感应炉熔炼,在氩气保护下浇铸成铸锭。将铸锭用单辊快淬设备重熔快淬,辊轮线速度为25m/s,将快淬态合金在氩气保护下用机械方法粉碎200目左右的粉末。取一定量的储氢合金粉末采用权利要求3所述KBH4碱溶液活化处理,然后进行苯加氢的实验,并同雷诺镍对苯加氢的实验结果进行了比较,结果如表1所示。可以看出MlNi3.12Co0.36Mn0.32Al1.2的活性与雷诺镍相当,而且由于铝的含量比雷诺镍中的铝的含量要低很多,使其自燃性明显低于雷诺镍.表1.MlNi3.12Co0.36Mn0.32Al1.2与雷诺镍对苯加氢的对比
催化剂 | 催化剂用量g | 苯用量ml | 反应温度℃ | 收率% |
MlNi3.12Co0.36Mn0.32Al1.2 | 5 | 200 | 170 | 46.8 |
雷诺镍 | 5 | 200 | 170 | 48.6 |
实施例3.
按合金设计的质量比[MlNi2.3Co0.4Mn0.3Al2]准确称取各组元纯金属(纯度均在99.0%以上),采用25kg真空感应炉熔炼,在氩气保护下浇铸成铸锭。将铸锭用单辊快淬设备重熔快淬,辊轮线速度为15m/s,将快淬态合金在氩气保护下用机械方法粉碎至小于200目。取一定量的储氢合金粉末采用如权利要求3所述的KBH4碱溶液活化处理,然后进行环己酮加氢的实验。实验结果表明(表2)该储氢合金对环己酮加氢的能力与雷诺镍相当。
表2.环己酮加氢反应的收率
催化剂 | 催化剂用量g | 反应温度℃ | 环己醇收率,% |
MlNi2.3Co0.4Mn0.3Al2 | 10 | 90 | 80.7 |
雷诺镍 | 10 | 90 | 81.5 |
Claims (4)
1、一种加氢反应催化剂——储氢合金,其特征在于:在CaCu5型六方结构储氢合金材料LaNi5的基础上,添加微量合金元素以改善其催化性能,化学式为MlCobMncAld,其中Ml为富La的混合稀土;2.10≤a≤4.20,0.30≤b≤0.45,0.20≤c≤0.45,0.30≤d≤2.0;a+b+c+d=5。
2、按权利要求1所述加氢反应催化剂——储氢合金的制备方法,其特征在于:母合金锭用真空感应熔炼制备;采用熔体旋转快淬法制成短条带或薄片,冷却方式为单辊快淬,辊轮线速度为10-35m/s;冷却速度为104-106℃/s;所得条带或薄片厚度为20-80μm,宽度为1-6mm。
3、按权利2要求所述加氢反应催化剂——储氢合金的制备方法,其特征在于:制备后,在氩气保护下球磨成200目左右的粉,并采用KBH4碱溶液对其进行活化处理。
4、按权利要求3所述加氢反应催化剂——储氢合金的制备方法,其特征在于:所述活化过程分两步进行;第一步:取0.1-0.5gKBH4加入100ml 5-10%(mol)KOH溶液中配成KBH4碱溶液,再将一定量的储氢合金粉末置于该溶液中,然后在水浴中加热并搅拌均匀后,在50-100℃下保温1-3小时;第二步:向处理液中再加入0.8-2.6g的KBH4,然后在50-100℃下保温2-4小时。
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CN101852565A (zh) * | 2010-05-11 | 2010-10-06 | 中国科学院广州能源研究所 | 储氢合金除氢长效热管 |
CN101450314B (zh) * | 2007-12-03 | 2012-03-07 | 比亚迪股份有限公司 | 储氢合金型加氢催化剂及其制备方法 |
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CN101450314B (zh) * | 2007-12-03 | 2012-03-07 | 比亚迪股份有限公司 | 储氢合金型加氢催化剂及其制备方法 |
CN101852565A (zh) * | 2010-05-11 | 2010-10-06 | 中国科学院广州能源研究所 | 储氢合金除氢长效热管 |
CN101852565B (zh) * | 2010-05-11 | 2012-07-04 | 中国科学院广州能源研究所 | 储氢合金除氢长效热管 |
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