CN111893360A - Ab5型储氢合金及其制备方法和应用以及含有机物氢气提纯方法 - Google Patents

Ab5型储氢合金及其制备方法和应用以及含有机物氢气提纯方法 Download PDF

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Publication number
CN111893360A
CN111893360A CN202010366678.7A CN202010366678A CN111893360A CN 111893360 A CN111893360 A CN 111893360A CN 202010366678 A CN202010366678 A CN 202010366678A CN 111893360 A CN111893360 A CN 111893360A
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equal
hydrogen
ltoreq
hydrogen storage
storage alloy
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CN111893360B (zh
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宋烨
林伟
杨雪
王磊
孙敏
刘俊
沈宁元
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

本发明涉及储氢合金领域，公开了AB5型储氢合金及其制备方法和应用以及含有机物氢气提纯方法，所述储氢合金具有AB5型晶体结构，其A位点含有La元素和Y元素，并且其B位点含有Ni元素；优选所述储氢合金的通式为：MmNix1Cox2Mnx3Fex4Alx5Snx6，Mm的通式为：Lay1Cey2Ndy3Pry4Yy5；3≤x1≤5.45，0≤x2≤1.5，0≤x3≤0.8，0≤x4≤0.8，0≤x5≤0.75，0≤x6≤0.2；0.4≤y1≤0.99，0≤y2≤0.45，0≤y3≤0.2，0≤y4≤0.05，0.01≤y5≤0.1。本发明提供的储氢合金，抗有机物能力强，且可以获得高压高纯度氢气。

Description

AB5型储氢合金及其制备方法和应用以及含有机物氢气提纯 方法
技术领域
本发明涉及储氢合金领域，具体涉及AB5型储氢合金及其制备方法和应用以及含有机物氢气提纯方法。
背景技术
氢气作为可再生能源，不仅能效高，而且几乎不产生废弃物。发展氢气能源有望成为提高能效、降低石油消费、改善生态环境、保障能源安全的重要途径，可持续、高效率的规模制氢技术的开发，已成为氢能时代的迫切需求。
利用氢能的技术例如燃料电池通常需要使用具有较高纯度的氢气，然而通常方法得到的氢气，其纯度比较低，特别是一些有机物转化过程产生的氢气例如催化裂化干气、甲烷转化产生的氢气、有机液体脱氢产生的氢气等，通常含有大量的有机物，无法直接使用，需要提纯后使用。氢气的提纯方法有多种，例如低温分离、膜分离、变压吸附分离。低温分离法的基本原理是在相同的压力下，利用氢气与其他组分的沸点差，采用降低温度的方法，使沸点较高的杂质部分冷凝下来，从而使氢与其他组分分离开来，得到纯度90-98％的氢气，但该种方法在分离之前，需要将先除去CO2、H2S和H2O，并且低温分离法仅适用于氢含量较低的气体。膜分离方法例如聚合物膜分离法纯化氢气的基本原理是：在工作压力下，气体通过聚合物膜的扩散速率不同，从而可以达到分离氢气的效果。其主要适用于以下情形：原料气的压力较高，原料气中氢浓度较高，对于富氢气体在低压条件下使用，对于贫氢气体在高压条件下使用，聚合物膜扩散法操作简单，适用范围较为广泛，同时氢气回收率也比较高，但是回收的氢气压力较低。变压吸附分离通过周期性改变压力来吸附和解吸，从而实现气体的分离和提纯，但变压吸附分离的产品回收率低，一般只有75％左右。
因此，急需开发一种新的有效氢气提纯方法。储氢合金在适当的温度和压力条件下，可以直接与氢气发生可逆反应，生成金属氢化物。它具有在降温升压时可以吸收氢，升温减压时释放氢的性质，同时表面具有很高的活性，利用储氢合金的这一性质，故而被用于纯化氢气。作为储氢合金，先已有以LaNi5为代表的AB5型合金、以ZrV0.4Ni1.5为代表的AB2型合金、此外还有AB型合金和A2B型合金等各种合金。
稀土储氢合金中典型代表是LaNi5。它的优点为活化容易，平台压力适中且平坦，吸/放氢平衡压差小，动力学性能优良，不易中毒。在25℃及0.2MPa压力下，该合金储氢量约为1.4％(本文中储氢量、储氢能力均为质量分数)，分解热为30kJ/mol H2，所以室温下便可以实现对氢的存储。此外，该合金还具有吸/放氢纯度高的特点(99.9％以上)，因此可以作为制备高纯度氢气的一种途径。LaNi5合金的缺点为抗粉化、抗氧化性能较差，且由于含有稀土元素La，价格偏高。对于稀土储氢合金的研究开发，应着重于通过更进一步调整和优化合金的化学组成，以及进一步优化合金的组织结构、合金的表面等，从而使合金的综合性能进一步得到提高。
文献(J.Alloysandcompounds,2003,Vol.354,pp310-314)公开了以Cr、Si取代AB5合金中的Co，虽然降低了成本，并且Cr元素替代可使合金活化次数减小，Si元素替代使储氢合金的循环性能改善，但是却使得最大放电容量和倍率性能变差。
目前虽然现开发了多种储氢合金，但是，目前利用储氢合金对含有机物的氢气进行提纯时，容易有机物中毒，使用寿命有待进一步提高。
发明内容
本发明的目的是为了克服现有技术存在的利用储氢合金对含有机物的氢气进行提纯时，储氢合金容易中毒，使用寿命较短的问题，提供一种储氢合金及其制备方法和应用以及含有机物氢气提纯方法。本发明提供的储氢合金在氢气中含有有机物的情况下具有较好吸氢效率和较长使用寿命，具有较好的抗有机物能力。
本发明的发明人在研究过程中发现，在具有AB5型晶体结构的储氢合金中，在A位点采用La元素和Y元素配合，协同B位点的Ni元素，可以有效对含有机物氢气进行提纯，且储氢合金具有较长的使用寿命。优选情况下，在B位点引入Al元素，有利于进一步提高储氢合金的抗有机物能力，具有更长的使用寿命。
为了实现上述目的，本发明第一方面提供一种储氢合金，其中，所述储氢合金具有AB5型晶体结构，其A位点含有La元素和Y元素，并且其B位点含有Ni元素。
优选地，所述B位点还含有Al元素。进一步优选地，Ni元素和Al元素的摩尔比为4-100：1，优选为20-50：1。
优选地，所述储氢合金的通式为：MmNix1Cox2Mnx3Fex4Alx5Snx6，Mm的通式为：Lay1Cey2Ndy3Pry4Yy5；
其中，4.5≤x1+x2+x3+x4+x5+x6≤5.5，3≤x1≤5.45，0≤x2≤1.5，0≤x3≤0.8，0≤x4≤0.8，0≤x5≤0.75，0≤x6≤0.2；
其中，y1+y2+y3+y4+y5＝1，0.4≤y1≤0.99，0≤y2≤0.45，0≤y3≤0.2，0≤y4≤0.05，0.01≤y5≤0.1。
本发明第二方面提供上述第一方面所述的储氢合金的制备方法，该方法包括以下步骤：
(1)以达到储氢合金组成的方式称量各储氢合金原料进行混合；
(2)将步骤(1)混合得到的物质进行熔炼，然后进行退火。
本发明第三方面提供上述第一方面所述的储氢合金在储氢过程中的应用。
本发明第四方面提供一种含有机物氢气提纯方法，包括：将含有机物的氢气与储氢合金接触，氢气与储氢合金进行反应形成含氢合金，然后使含氢合金释放氢气，收集释放的氢气，其中，所述的储氢合金为上述第一方面所述的储氢合金。
本发明提供的储氢合金，吸氢效率高，抗有机物能力强，在氢气中含有机物的情况下，具有较高的储氢量，可以获得高压高纯度氢气。例如，采用本发明实施例4提供的储氢合金，可以得到压力为10MPa，纯度高达99.97％的氢气，且储氢合金的十次吸氢量可以达到104.98g，衰减率仅为0.04％。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本发明第一方面提供一种储氢合金，所述储氢合金具有AB5型晶体结构，其A位点含有La元素和Y元素，并且其B位点含有Ni元素。
根据本发明提供的储氢合金，所述储氢合金具有AB5型晶体结构，所述储氢合金的含有La元素和Y元素，并且含有Ni元素，且Ni元素与La元素和Y元素的总量的摩尔比为4.5-5.5:1。
本发明的发明人在研究过程中发现，在具有AB5型晶体结构的储氢合金中，在A位点采用La元素和Y元素配合，协同B位点的Ni元素，可以有效对含有机物氢气进行提纯，且储氢合金具有较长的使用寿命。
优选情况下，La元素和Y元素的摩尔比为20-99：1，优选为16-50：1。例如可以为16:1、20:1、25:1、30:1、35:1、40:1、45:1、50:1，以及任意两组数之间的任意值。二者以该优选比例配合使用，储氢合金的吸氢效率更高，抗有机物能力更强，在氢气中含有机物的情况下，具有更高的储氢量。
优选情况下，所述B位点还含有Al元素。在B位点引入Al元素，有利于进一步提高储氢合金对含有机物氢气的提纯效率和使用寿命。
本发明对Al元素的含量选择范围较宽，可以根据B位点中Ni元素的含量进行适当的选择，优选地，Ni元素和Al元素的摩尔比为4-100：1，更优选为20-50：1。例如可以为20:1、25:1、30:1、35:1、40:1、45:1、50:1，以及任意两组数之间的任意值。二者以该优选比例配合使用，储氢合金的吸氢效率更高，抗有机物能力更强，在氢气中含有机物的情况下，具有更高的储氢量。
根据本发明，所述A位点中还可以含有其他稀土金属元素，所述其他稀土金属元素包括但不限于Ce(铈)、Pr(镨)、Nd(钕)、Pm(钷)、Sm(钐)、Eu(铕)、Gd(钆)、Tb(铽)、Dy(镝)、Ho(钬)、Er(铒)、Tm(铥)、Yb(镱)、Lu(镥)、钪(Sc)元素。优选地，所述A位点中还含有Ce元素更有利于提高储氢合金的储氢量，吸氢效率更高，抗有机物能力更强。
根据本发明，所述B位点中还可以含有Co、Mn、Fe、Sn元素中的至少一种。Co、Mn、Fe、Sn元素中的至少一种的加入更有利于调整吸氢压力。
根据本发明的一种优选实施方式，所述储氢合金的通式为：MmNix1Cox2Mnx3Fex4Alx5Snx6，Mm的通式为：Lay1Cey2Ndy3Pry4Yy5；其中，4.5≤x1+x2+x3+x4+x5+x6≤5.5，3≤x1≤5.45，0≤x2≤1.5，0≤x3≤0.8，0≤x4≤0.8，0≤x5≤0.75，0≤x6≤0.2；其中，y1+y2+y3+y4+y5＝1，0.4≤y1≤0.99，0≤y2≤0.45，0≤y3≤0.2，0≤y4≤0.05，0.01≤y5≤0.1。
上述通式中x1、x2、x3、x4、x5、x6分别表示相对于1摩尔的Mm，Ni、Co、Mn、Fe、Al、Sn的摩尔数。y1、y2、y3、y4、y5分别表示在1摩尔的Mm中，La、Ce、Nd、Pr、Y的摩尔数。后续通式具有该示例类似的含义，本发明不作赘述。
根据本发明的一种优选实施方式，其中，x2、x3、x4、x6的值不同时为零。
根据本发明的另一种优选实施方式，其中，y2、y3、y4的值不同时为零。
根据本发明，优选地，3≤x1≤4.9，进一步优选地，3.5≤x1≤4.8，例如x1可以为3.5、3.6、3.7、3.8、3.9、4.0、4.1、4.2、4.3、4.4、4.5、4.6、4.7、4.8，以及任意两组数之间的任意值。
根据本发明，优选地，0.1≤x2≤1，例如，x2可以为0、0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9、1.0，以及任意两组数之间的任意值。
根据本发明，优选地，0.1≤x3≤0.6，例如，x3可以为0.1、0.2、0.3、0.4、0.5、0.6，以及任意两组数之间的任意值。
根据本发明，优选地，0.1≤x4≤0.6，例如，x4可以为0.1、0.2、0.3、0.4、0.5、0.6，以及任意两组数之间的任意值。
根据本发明，优选地，0.05≤x5≤0.5，例如，x5可以为0.05、0.1、0.15、0.2、0.25、0.3、0.35、0.4、0.45、0.5，以及任意两组数之间的任意值。
根据本发明，优选地，0≤x6≤0.15，例如，x6可以为0、0.01、0.02、0.03、0.04、0.05、0.06、0.07、0.08、0.09、0.1、0.11、0.12、0.13、0.14、0.15，以及任意两组数之间的任意值。
根据本发明，优选地，0.4≤y1≤0.8，例如，y1可以为0.4、0.45、0.5、0.55、0.6、0.65、0.7、0.75、0.8，以及任意两组数之间的任意值。
根据本发明，优选地，0.1≤y2≤0.45，例如，y2可以为0.1、0.15、0.2、0.25、0.3、0.35、0.4、0.45，以及任意两组数之间的任意值。
根据本发明，优选地，0≤y3≤0.2，例如，y3可以为0、0.1、0.15、0.2，以及任意两组数之间的任意值。
根据本发明，优选地，0≤y4≤0.05，例如，y4可以为0、0.01、0.02、0.03、0.04、0.05，以及任意两组数之间的任意值。
根据本发明，优选地，0.01≤y5≤0.05，例如，y5可以为0.01、0.02、0.03、0.04、0.05，以及任意两组数之间的任意值。
根据本发明的一种特别优选实施方式，所述储氢合金的通式为La0.5Ce0.32Nd0.15Pr0.02Y0.01Ni4.4Fe0.55Al0.05、La0.5Ce0.32Nd0.15Pr0.02Y0.01Ni4.4Fe0.6、La0.8Ce0.15Y0.05Ni4Mn0.5Al0.5、La0.8Ce0.15Y0.05Ni4.5Mn0.5、La0.45Ce0.4Nd0.1Pr0.03Y0.02Ni4Co0.8Al0.2、La0.45Ce0.4Nd0.1Pr0.03Y0.02Ni4.2Co0.8、La0.75Ce0.15Nd0.05Pr0.02Y0.03Ni4.7Al0.1Fe0.2、La0.75Ce0.15Nd0.05Pr0.02Y0.03Ni4.8Fe0.2、La0.8Ce0.15Nd0.03Y0.02Ni4.5Co0.3Mn0.1Al0.1、La0.8Ce0.15Nd0.03Y0.02Ni4.5Co0.4Mn0.1和La0.97Y0.03Ni4Co1中的至少一种；更优选地，La0.5Ce0.32Nd0.15Pr0.02Y0.01Ni4.4Fe0.55Al0.05、La0.8Ce0.15Y0.05Ni4Mn0.5Al0.5、La0.45Ce0.4Nd0.1Pr0.03Y0.02Ni4Co0.8Al0.2、La0.75Ce0.15Nd0.05Pr0.0 2Y0.03Ni4.7Al0.1Fe0.2和La0.8Ce0.15Nd0.03Y0.02Ni4.5Co0.3Mn0.1Al0.1中的至少一种。
本发明对上述储氢合金的制备方法不做特别限定，现有能够制备得到上述组成的储氢合金的方法均在本发明的保护范围之内。
本发明第二方面提供上述第一方面所述的储氢合金的制备方法，该方法包括以下步骤：
(1)以达到储氢合金组成的方式称量各储氢合金原料进行混合；
(2)将步骤(1)混合得到的物质进行熔炼，然后进行退火。
本发明对步骤(1)所述混合的方式没有特别的限定，只要上述各储氢合金原料的用量能够使得制得的储氢合金的组成满足上述限定即可。所述各储氢合金原料可以为上述组成所述的各种金属。
本发明对所述熔炼的方式和条件选择范围较宽，现有各种熔炼方式和条件均在本发明保护范围之内，所述熔炼包括但不限于电炉熔炼、感应熔炼。所述电炉熔炼、感应熔炼具有本领域的常规示意，本发明在此不再赘述。
根据本发明的一种优选实施方式，所述熔炼的条件包括：在真空或者惰性气氛下进行，温度为1200-3000℃，优选为1800-2200℃。
根据本发明的一种优选实施方式，所述熔炼在真空下进行，所述熔炼的压力为1×10-5-1×10-3Pa，优选为0.5×10-4-5×10-4Pa。
根据本发明的一种优选实施方式，所述熔炼在惰性气氛下进行，所述熔炼的压力为0.5-1bar，优选为0.7-1bar。
本发明中，所述压力均为绝压。
根据本发明，优选地，所述熔炼的时间为0.5-3h，进一步优选为0.5-2h。
所述惰性气氛可以由惰性气体提供，所述惰性气体包括但不限于氩气、氦气、氖气中的至少一种。优选地，所述惰性气氛由氩气提供。
根据本发明提供的方法，优选地，该方法还包括将熔炼得到的物质进行冷却，然后进行所述退火。所述冷却可以冷却至室温(例如25℃)至所述退火温度之间的任一温度。所述冷却优选在惰性气氛下进行。所述惰性气氛的选择如上所述，在此不再赘述。
根据本发明的一种优选实施方式，所述冷却采用快速冷却，即从熔炼温度冷却至500℃的时间不超过1分钟。
根据本发明，优选地，所述退火的条件包括：在真空或者氩气气氛下进行，温度为700-1000℃，时间为12-360小时，进一步优选地，温度为800-980℃，时间为24-240小时。所述退火的压力可以真空-0.1MPa。所述退火可以在高真空退火炉中进行。
根据本发明，优选地，该方法还包括将步骤(2)退火得到的物质降温后进行破碎得到所需大小的产品。优选情况下，可以将步骤(2)退火得到的物质降至室温后进行破碎。更优选情况下，将步骤(2)退火得到的物质降至室温后进行破碎处理以得到10-400目、优选为70-200目的产品。本发明对提供上述大小的产品的具体方式不作特别限定，例如可以为粉碎过筛。
根据本发明，优选地，该方法还包括将得到的储氢合金在使用前进行活化处理。本发明对所述活化处理的没有特别的限定，可以按照本领域常规技术手段进行。例如所述活化处理包括但不限于热活化和吸放氢活化。所述吸放氢活化的次数可以为一次或者一次以上，例如2-4次。
优选地，所述活化处理的条件包括：在真空下，温度为50-300℃，时间为1-10小时；进一步优选地，所述活化处理的条件包括：在真空下，温度为80-300℃，时间为2-8小时。
本发明第三方面提供上述第一方面所述的储氢合金在储氢过程中的应用。采用本发明提供的储氢合金，在储氢过程中，具有较好吸氢效率，有利于得到纯度更高的氢气，另外，其抗有机物能力强，具有较长的使用寿命。
本发明第四方面提供一种含有机物氢气提纯方法，包括：将含有机物的氢气与储氢合金接触，氢气与储氢合金进行反应形成含氢合金，然后使含氢合金释放氢气，收集释放的氢气，其中，所述的储氢合金为上述第一方面所述的储氢合金。
本发明提供的储氢合金特别适合对含有机物的氢气进行提纯，本发明对所述含有机物的氢气的来源选择范围不作特别限定，其可以来自现有技术中有机物转化过程得到的含有机物氢气，包括但不限于催化裂化干气、甲烷转化产生的氢气、有机液体脱氢产生的氢气。
根据本发明，所述含有机物的氢气与储氢合金可以在储氢罐中进行所述接触。
根据本发明，优选地，所述含有机物的氢气的温度为-20℃至70℃，进一步优选为0-30℃。
根据本发明，优选地，所述含有机物的气体中有机物的含量不超过1体积％，例如为0.05-0.5体积％。
本发明对所述有机物的种类不做特别限定，可以为上述催化裂化干气、甲烷转化生产氢气、有机液体脱氢生产氢气过程中氢气中可能含有的各种有机物。例如，所述有机物包括但不限于甲苯、甲烷、环己烷、甲基环己烷、苯和乙烷。
根据本发明的一种优选实施方式，待储氢合金储氢量达到理论容量的75％以上时，然后使含氢合金释放氢气。
根据本发明的一种优选实施方式，储氢合金储氢量达到理论容量的75％以上时，停止通入含有机物的气体。
本发明对使含氢合金释放氢气的方式没有特别的限定，例如可以采用加热的方式。优选加热至20-350℃。在高于平衡压力温度以上进行金属氢化物的氢气解析。当储氢罐放氢总量达到吸氢总量的90％时，停止放氢。
本发明提供的提纯方法中，可以多个储氢罐并联操作，储氢罐可以分别次序吸氢和放氢，也可以几个同时吸氢和放氢，但是不能全部同时都在吸氢或者同时在放氢。
以下将通过实施例对本发明进行详细描述。
以下实施例中，无特殊说明下，所述室温指的是25℃。
实施例1-5
按照合金成分称取金属共计约1000g，置于电弧熔炼炉的水冷坩埚中，在氩气气氛下熔炼得到合金，具体制备过程：高纯Ar气氛(纯度99.999％)
下，进行熔炼，熔炼的温度、压力和时间如表1所示；在Ar气氛下自然冷却至室温，然后转移至真空退火炉中进行真空退火，背景压力为1×10-4Pa，所述退火的温度、时间如表1所示；自然冷却至室温。将得到的合金粉碎过筛，得到70-200目的金属粉末，将粉末装入储氢罐中，将储氢罐在0.1Pa真空下加热至50-300℃保温1-10h对合金粉末进行活化(活化的具体温度和时间如表1所示)，得到储氢合金C1-C5。储氢合金C1-C5的表达式如表1所示。
实施例6-10
实施例6-10储氢合金的制备条件分别与实施例1-5相同，不同的是，储氢合金的组成，实施例6-10制得的储氢合金C6-C10的表达式如表2所示。
实施例11
按照实施例1的方法制备储氢合金，不同的是，储氢合金的组成，实施例11制得的储氢合金C11的表达式如表2所示。
对比例1-5
对比例1-5储氢合金的制备条件分别与实施例1-5相同，不同的是，储氢合金的组成，对比例1-5制得的储氢合金DC1-DC5的表达式如表3所示。
表1
Figure BDA0002476721510000111
Figure BDA0002476721510000121
表2
Figure BDA0002476721510000122
表3
Figure BDA0002476721510000123
测试例1
对上述实施例和对比例制得的合金的储氢性能进行评价，具体包括：
将1kg储氢合金置于储氢罐中，将20℃的含有机物氢气(甲烷含量为0.1体积％)作为模型化合物，在压力2MPa通入储氢罐中，使得氢气与储氢合金进行反应形成含氢合金，待储氢合金储氢量达到理论容量的75％，停止通入含有机物氢气，并用纯度95％的氢气进行吹扫20min，然后对储氢罐进行加热，保持储氢合金在10MPa下进行持续放氢，氢气纯度采用气相色谱进行分析。氢气纯度列于表4中。循环上述吸氢和放氢10次后，测定累计储氢量和储氢量衰减率，列于表4中，所述衰减率＝(第一次吸放氢储氢量-第十次吸放氢储氢量)/第一次吸放氢储氢量×100％。累计储氢量是指十次吸氢量的总和。
表4
累计储氢量，g 氢气纯度，％ 衰减率，％
实施例1 104.75 ≥99.97 0.48
实施例2 104.90 ≥99.97 0.20
实施例3 104.86 ≥99.97 0.27
实施例4 104.98 ≥99.97 0.04
实施例5 104.95 ≥99.97 0.09
实施例6 104.63 ≥99.97 0.70
实施例7 104.80 ≥99.97 0.38
实施例8 104.76 ≥99.97 0.45
实施例9 104.95 ≥99.97 0.09
实施例10 104.86 ≥99.97 0.27
实施例11 104.39 ≥99.97 1.16
对比例1 101.39 99.76 6.80
对比例2 102.07 99.83 5.53
对比例3 101.89 99.56 5.87
对比例4 102.62 99.85 4.50
对比例5 102.12 99.89 5.44
通过表4的结果可以看出，本发明提供的储氢合金，可以得到压力为10MPa，纯度高达99.97％的氢气，且储氢合金储氢量大，抗有机物能力强，循环上述吸氢和放氢10次后，衰减率在1.16％以下，优选方案中，衰减率为0.7％以下。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (12)

1.一种储氢合金，所述储氢合金具有AB5型晶体结构，其A位点含有La元素和Y元素，并且其B位点含有Ni元素。
2.根据权利要求1所述的储氢合金，其中，La元素和Y元素的摩尔比为20-99：1，优选为16-50：1；
优选地，所述B位点还含有Al元素；进一步优选地，Ni元素和Al元素的摩尔比为4-100：1，优选为20-50：1。
3.根据权利要求1所述的储氢合金，其中，所述储氢合金的通式为：MmNix1Cox2Mnx3Fex4Alx5Snx6，Mm的通式为：Lay1Cey2Ndy3Pry4Yy5；
其中，4.5≤x1+x2+x3+x4+x5+x6≤5.5，3≤x1≤5.45，0≤x2≤1.5，0≤x3≤0.8，0≤x4≤0.8，0≤x5≤0.75，0≤x6≤0.2；
其中，y1+y2+y3+y4+y5＝1，0.4≤y1≤0.99，0≤y2≤0.45，0≤y3≤0.2，0≤y4≤0.05，0.01≤y5≤0.1；
其中，x1、x2、x3、x4、x5、x6分别表示相对于1摩尔的Mm，Ni、Co、Mn、Fe、Al、Sn的摩尔数；y1、y2、y3、y4、y5分别表示在1摩尔的Mm中，La、Ce、Nd、Pr、Y的摩尔数。
4.根据权利要求3所述的储氢合金，其中，3≤x1≤4.9，0.1≤x2≤1，0.1≤x3≤0.6，0.1≤x4≤0.6，0.05≤x5≤0.5，0≤x6≤0.15；
优选地，0.4≤y1≤0.8，0.1≤y2≤0.45，0≤y3≤0.2，0≤y4≤0.05，0.01≤y5≤0.05。
5.根据权利要求1所述的储氢合金，其中，所述储氢合金的通式为La0.5Ce0.32Nd0.15Pr0.0 2Y0.01Ni4.4Fe0.55Al0.05、La0.5Ce0.32Nd0.15Pr0.02Y0.01Ni4.4Fe0.6、La0.8Ce0.15Y0.05Ni4Mn0.5Al0.5、La0.8Ce0.15Y0.05Ni4.5Mn0.5、La0.45Ce0.4Nd0.1Pr0.03Y0.02Ni4Co0.8Al0.2、La0.45Ce0.4Nd0.1Pr0.03Y0.02Ni4.2Co0.8、La0.75Ce0.15Nd0.05Pr0.02Y0.03Ni4.7Al0.1Fe0.2、La0.75Ce0.15Nd0.05Pr0.02Y0.03Ni4.8Fe0.2、La0.8Ce0.15Nd0.03Y0.02Ni4.5Co0.3Mn0.1Al0.1、La0.8Ce0.15Nd0.03Y0.02Ni4.5Co0.4Mn0.1和La0.97Y0.03Ni4Co1中的至少一种；更优选地，La0.5Ce0.32Nd0.15Pr0.02Y0.01Ni4.4Fe0.55Al0.05、La0.8Ce0.15Y0.05Ni4Mn0.5Al0.5、La0.45Ce0.4Nd0.1Pr0.03Y0.02Ni4Co0.8Al0.2、La0.75Ce0.15Nd0.05Pr0.0 2Y0.03Ni4.7Al0.1Fe0.2和La0.8Ce0.15Nd0.03Y0.02Ni4.5Co0.3Mn0.1Al0.1中的至少一种。
6.权利要求1-5中任意一项所述的储氢合金的制备方法，该方法包括以下步骤：
(1)以达到储氢合金组成的方式称量各储氢合金原料进行混合；
(2)将步骤(1)混合得到的物质进行熔炼，然后进行退火。
7.根据权利要求6所述的制备方法，其中，所述熔炼为电炉熔炼或者感应熔炼；
优选地，所述熔炼的条件包括：在真空或者惰性气氛下进行，温度为1200-3000℃，优选为1800-2200℃；
优选地，在真空下进行，所述熔炼的压力为1×10-5-1×10-3Pa，优选为0.5×10-4-5×10-4Pa；
优选地，在惰性气氛下进行，所述熔炼的压力为0.5-1bar，优选为0.7-1bar。
8.根据权利要求6所述的制备方法，其中，所述退火的条件包括：在真空或者氩气气氛下进行，温度为700-1000℃，时间为12-360小时。
9.根据权利要求6-8中任意一项所述的制备方法，其中，该方法还包括将步骤(2)退火得到的物质降温后进行破碎处理以得到10-400目的产品。
10.根据权利要求6-9中任意一项所述的制备方法，其中，该方法还包括将步骤(2)退火得到的物质进行活化处理；
优选地，所述活化处理的条件包括：在真空下，温度为50-300℃，时间为1-10小时。
11.权利要求1-5中任意一项所述储氢合金在储氢过程中的应用。
12.一种含有机物氢气提纯方法，包括：将含有机物的氢气与储氢合金接触，氢气与储氢合金进行反应形成含氢合金，然后使含氢合金释放氢气，收集释放的氢气，其中，所述的储氢合金为权利要求1-5中任意一项所述储氢合金。
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US20220227623A1 (en) 2022-07-21
CN111893359B (zh) 2022-10-21
CN111893361B (zh) 2022-02-08
CN111893361A (zh) 2020-11-06
AU2020269473A1 (en) 2021-12-16
TW202106611A (zh) 2021-02-16
JP2022531797A (ja) 2022-07-11
CN111893360B (zh) 2022-10-21
CN111892019B (zh) 2022-09-27
CN111893346B (zh) 2022-10-21
EP3967783A4 (en) 2023-08-09
CN111892017B (zh) 2022-10-21
WO2020224586A1 (zh) 2020-11-12
CN111892016A (zh) 2020-11-06
AU2020267541A1 (en) 2021-12-16
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CN111893347A (zh) 2020-11-06
KR20220005088A (ko) 2022-01-12

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