CN111893346A - 固溶体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

固溶体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
CN111893346A
CN111893346A CN202010368035.6A CN202010368035A CN111893346A CN 111893346 A CN111893346 A CN 111893346A CN 202010368035 A CN202010368035 A CN 202010368035A CN 111893346 A CN111893346 A CN 111893346A
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equal
ltoreq
hydrogen
hydrogen storage
less
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CN111893346B (zh
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林伟
宋海涛
杨雪
宋烨
孙敏
刘俊
王磊
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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，公开了一种固溶体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，所述储氢合金的表达式为：Ax1Bx2，0.7≤x1≤0.95，0.05≤x2≤0.3；A为Tiy1Vy2Zry3Nby4Yy5Lay6Cay7，0.45≤y1≤0.9，0≤y2≤0.5，0≤y3≤0.5，0≤y4≤0.55，0≤y5≤0.2，0≤y6≤0.1，0≤y7≤0.1；B为Mnz1Fez2Coz3Niz4，0.55≤z1+z2≤1，0≤z3≤0.3，0≤z4≤0.45。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。

Description

固溶体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，具体涉及固溶体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。
储氢合金是一种新型合金，一定条件下能吸收氢气，一定条件能放出氢气。利用储氢合金对氢原子有特殊的亲和力，而对其他气体杂质择优排斥的特性，即利用储氢合金具有只选择吸收氢和捕获不纯杂质的功能，不但可以回收废气中的氢，而且可以使氢纯度高于95％以上，价格便宜、安全，具有十分重要的社会效益和经济意义。
固溶体型合金具有储氢量大、氢在氢化物中的扩散速度较快等优点，已应用于氢的贮存、净化、压缩以及氢的同位素分离等领域，其缺点是合金充放电的循环稳定性较差，循环容量衰减速度较快的问题。固溶体型储氢合金的储氢量、平台压及其循环性能受合金成分影响较大。
CN102443730A公开了一种储氢合金，其分子通式为CouFevMnwTixVyZrz，其中0.5≤u≤2.0，0.5≤v≤2.5，0.5≤w≤2.0，0.5≤x≤2.5，0.4≤y≤3.0，0.4≤z≤3.0。其可以达到使该储氢合金在常温常压的工作环境下，具有高吸氢/放氢和储氢的能力，使其具有发展成为绿色环保能源的潜质。
CN106801177A公开了一种V-Fe系固溶体型储氢合金及其制备方法。该储氢合金的化学式为(VuFev)100-x-yTixMy-Rez，其中x、y、z分别表示Ti、M、Re的原子数，x＝5-30，y＝0-10，z＝1-3，u、v分别为V、Fe在V-Fe中间合金中的原子数百分比，u+v＝1，u/v＝5-6；M为Cr、Mn、Fe、Co、Ni、Mo、W、Ta、Nb和Al中的一种或两种以上的组合，Re代表稀土元素。其大幅降低了钒基储氢合金成本，有效改善了合金的吸放氢动力学、循环寿命，从而提高了材料的综合储氢性能。
但是，目前大多数的储氢合金例如LaNi5，TiFe，TiMn2应用于提纯含有机物的氢气时，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，提供一种固溶体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。本发明提供的储氢合金抗有机物能力强，对含有机物氢气进行提纯时，使用寿命较长。
为了实现上述目的，本发明一方面提供一种固溶体型储氢合金，所述储氢合金的表达式为：Ax1Bx2，其中，x1、x2分别表示A和B的摩尔数，x1+x2＝1，0.7≤x1≤0.95，0.05≤x2≤0.3；
其中，A的表达式为Tiy1Vy2Zry3Nby4Yy5Lay6Cay7，y1+y2+y3+y4+y5+y6+y7＝1，y1、y2、y3、y4、y5、y6、y7分别表示Ti、V、Zr、Nb、Y、La、Ca的摩尔数，其中，0.45≤y1≤0.9，0≤y2≤0.5，0≤y3≤0.5，0≤y4≤0.55，0≤y5≤0.2，0≤y6≤0.1，0≤y7≤0.1；
B的表达式为Mnz1Fez2Coz3Niz4，其中，z1+z2+z3+z4＝1，z1、z2、z3、z4分别表示Mn、Fe、Co和Ni的摩尔数，其中，0≤z1≤1，0≤z2≤0.95，且0.55≤z1+z2≤1，0≤z3≤0.3，0≤z4≤0.45。
优选地，0.9≤x1≤0.95，0.05≤x2≤0.1。
优选地，0.01≤y5≤0.2。
优选地，0.05≤z4≤0.45，更优选0.05≤z4≤0.3。
本发明第二方面提供上述第一方面所述的固溶体型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固溶体型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，所述的储氢合金为前述第一方面所述的固溶体型储氢合金。
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6提供的储氢合金，可以得到压力为50MPa，纯度高达99.95％的氢气，且储氢合金的三十次吸氢量可以达到583.31g，且衰减率仅为0.58％。
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固溶体型储氢合金，所述储氢合金的表达式为：Ax1Bx2，其中，x1、x2分别表示A和B的摩尔数，x1+x2＝1，0.7≤x1≤0.95，0.05≤x2≤0.3；
其中，A的表达式为Tiy1Vy2Zry3Nby4Yy5Lay6Cay7，y1+y2+y3+y4+y5+y6+y7＝1，y1、y2、y3、y4、y5、y6、y7分别表示Ti、V、Zr、Nb、Y、La、Ca的摩尔数，其中，0.45≤y1≤0.9，0≤y2≤0.5，0≤y3≤0.5，0≤y4≤0.55，0≤y5≤0.2，0≤y6≤0.1，0≤y7≤0.1；
B的表达式为Mnz1Fez2Coz3Niz4，其中，z1+z2+z3+z4＝1，z1、z2、z3、z4分别表示Mn、Fe、Co和Ni的摩尔数，其中，0≤z1≤1，0≤z2≤0.95，且0.55≤z1+z2≤1，0≤z3≤0.3，0≤z4≤0.45。
根据本发明一种优选实施方式，其中，0.8≤x1≤0.95，0.05≤x2≤0.2。为了更进一步提高储氢合金的抗有机物中毒能力，优选地，0.9≤x1≤0.95，0.05≤x2≤0.1。
在本发明中，优选情况下，y2、y3、y4、y5、y6、y7不同时为零，更优选情况下，y2、y3、y4、y6、y7不同时为零。
在本发明中，优选情况下，z3、z4不同时为零。
根据本发明，优选地，0.5≤y1≤0.8，例如y1可以为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≤y2≤0.4，例如y2可以为0、0.15、0.2、0.25、0.3、0.35、0.4，以及任意两组数之间的任意值。
根据本发明，优选地，0≤y3≤0.4，例如y3可以为0、0.15、0.2、0.25、0.3、0.35、0.4，以及任意两组数之间的任意值。
根据本发明，优选地，0≤y4≤0.4，例如y4可以为0、0.15、0.2、0.25、0.3、0.35、0.4，以及任意两组数之间的任意值。
根据本发明，优选地，0.01≤y5≤0.2，更优选为0.05≤y5≤0.2，例如y5可以为0.01、0.02、0.04、0.06、0.08、0.1、0.12、0.14、0.16、0.18、0.2，以及任意两组数之间的任意值。
根据本发明，优选地，0≤y6≤0.05，例如y6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，优选地，0≤y7≤0.05，例如y7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。
本发明在研究过程中发现，在上述固溶体型储氢合金中，B中含有Mn时，抗有机物中毒能力更强。优选地，0.1≤z1≤1，更优选为0.2≤z1≤0.95，例如z1可以为0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9、0.95，以及任意两组数之间的任意值。
本发明对z2的选择范围较宽，只要满足0.55≤z1+z2≤1即可。优选地，0≤z2≤0.9，例如z2可以为0、0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9，以及任意两组数之间的任意值。
根据本发明，优选地，0≤z3≤0.2，例如z3可以为0、0.02、0.04、0.06、0.08、0.1、0.12、0.14、0.16、0.18、0.2，以及任意两组数之间的任意值。
根据本发明，优选地，0.05≤z4≤0.45，更优选为0.05≤z4≤0.3，例如z4可以为0.05、0.1、0.15、0.2、0.25、0.3，以及任意两组数之间的任意值。
本发明的发明人在研究过程中发现，在固溶体型储氢合中，采用Ti配合Y、Ni、Mn元素按照上述优选含量配合能够进一步提高抗有机物污染性能，特别适合于工业应用。
根据本发明的一种优选实施方式，所述储氢合金的通式为(Ti0.8V0.2)0.95(Fe1)0.05、(Ti0.8Y0.2)0.95(Mn0.95Ni0.05)0.05、(Ti0.4V0.4Y0.2)0.9(Fe0.05Mn0.95)0.1、(Ti0.4V0.4Y0.2)0.9(Fe0.05Mn0.9Ni0.05)0.1、(Ti0.7Nb0.1Y0.2)0.9(Mn1)0.1、(Ti0.7Nb0.1Y0.2)0.9(Mn0.7Ni0.3)0.1、(Ti0.4Zr0.4Y0.2)0.93(Fe0.2Mn0.7Co0.1)0.07、(Ti0.4Zr0.4Y0.2)0.93(Fe0.2Mn0.7Ni0.1)0.07、(Ti0.4V0.4Zr0.2)0.95(Fe0.6Mn0.2Co0.1Ni0.1)0.05、(Ti0.4V0.35Zr0.2Y0.05)0.95(Fe0.6Mn0.2Co0.1Ni0.1)0.05、(Ti0.88Y0.1Ca0.02)0.95(Fe0.3Mn0.6Co0.1)0.05和(Ti0.88Y0.1Ca0.02)0.95(Fe0.3Mn0.6Ni0.1)0.05中的至少一种。
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(Ti0.8Y0.2)0.95(Mn0.95Ni0.05)0.05、(Ti0.4V0.4Y0.2)0.9(Fe0.05Mn0.9Ni0.05)0.1、(Ti0.7Nb0.1Y0.2)0.9(Mn0.7Ni0.3)0.1、(Ti0.4Zr0.4Y0.2)0.93(Fe0.2Mn0.7Ni0.1)0.07、(Ti0.4V0.35Zr0.2Y0.05)0.95(Fe0.6Mn0.2Co0.1Ni0.1)0.05和(Ti0.88Y0.1Ca0.02)0.95(Fe0.3Mn0.6Ni0.1)0.05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。
根据本发明，优选地，所述熔炼的时间为0.1-3h，进一步优选为10-60min。
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：在真空或者惰性气氛下进行，温度为700-1000℃，时间为12-360小时，进一步优选地，温度为800-950℃，时间为24-168小时。所述退火的压力不高于0.1MPa。所述退火可以在高真空退火炉中进行。
本发明中，所述的压力均为绝压。
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20-400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，该方法还包括将步骤(2)退火得到的物质进行活化处理。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100-300℃，时间为1-4小时。
本发明第三方面提供上述第一方面所述的固溶体型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，不但有利于得到纯度更高的氢气，且抗有机物中毒能力强，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吸附反应形成含氢合金，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固溶体型储氢合金。
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0.01-0.5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1-6
按照合金成分称取金属共计约1000g，置于真空感应熔炼炉的水冷坩埚中，在真空下熔炼得到合金，制备条件包括：在背景真空1×10-4Pa下进行，熔炼温度和时间如表1所示；在背景真空1×10-4Pa下以10℃/min的速率降温至退火温度，进行退火，所述退火的温度、时间如表1所示；在背景真空1×10-4Pa下自然冷却至室温。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300℃保温4h对合金粉末进行活化，得到储氢合金C1-C6。储氢合金C1-C6的表达式如表1所示。
实施例7-12
实施例7-12储氢合金的制备条件分别与实施例1-6相同，不同的是，储氢合金的组成，实施例7-12得的储氢合金C7-C12的表达式如表2所示。
实施例13
实施例13储氢合金的制备条件与实施例3相同，不同的是，储氢合金的组成，实施例13制得的储氢合金C13的表达式为(Ti0.7Nb0.1Y0.2)0.8(Mn0.7Ni0.3)0.2。
对比例1-2
对比例1-2储氢合金的制备条件分别与实施例1-2相同，不同的是，储氢合金的组成，对比例1-2制得的储氢合金DC1和DC2的表达式如表3所示。
对比例3
对比例3储氢合金的制备条件与实施例4相同，不同的是，储氢合金的组成，对比例3制得的储氢合金DC3的表达式如表3所示。
对比例4
对比例4储氢合金的制备条件与实施例5相同，不同的是，储氢合金的组成，对比例4制得的储氢合金DC4的表达式如表3所示。
表1
Figure BDA0002477185500000111
表2
Figure BDA0002477185500000112
表3
Figure BDA0002477185500000113
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0.01体积％)作为模型化合物，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50MPa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、累计储氢量和储氢量衰减率列于表4中。累计储氢量是指三十次吸氢的总量。循环上述吸氢和放氢三十次后，测定储氢量的衰减率，所述衰减率＝(第一次吸放氢储氢量-第三十次吸放氢储氢量)/第一次吸放氢储氢量×100％。
表4
Figure BDA0002477185500000121
Figure BDA0002477185500000131
通过表4的结果可以看出，本发明提供的储氢合金，可以得到高纯(≥99.95)高压(50MPa)的氢气，具有较好的提纯增压效果。另外，本发明提供的储氢合金抗有机物能力强，循环上述吸氢和放氢30次后，衰减率在2.04％以下，优选方案中，衰减率为1.27％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)

1.一种固溶体型储氢合金，所述储氢合金的表达式为：Ax1Bx2，其中，x1、x2分别表示A和B的摩尔数，x1+x2＝1，0.7≤x1≤0.95，0.05≤x2≤0.3；
其中，A的表达式为Tiy1Vy2Zry3Nby4Yy5Lay6Cay7，y1+y2+y3+y4+y5+y6+y7＝1，y1、y2、y3、y4、y5、y6、y7分别表示Ti、V、Zr、Nb、Y、La、Ca的摩尔数，其中，0.45≤y1≤0.9，0≤y2≤0.5，0≤y3≤0.5，0≤y4≤0.55，0≤y5≤0.2，0≤y6≤0.1，0≤y7≤0.1；
B的表达式为Mnz1Fez2Coz3Niz4，其中，z1+z2+z3+z4＝1，z1、z2、z3、z4分别表示Mn、Fe、Co和Ni的摩尔数，其中，0≤z1≤1，0≤z2≤0.95，且0.55≤z1+z2≤1，0≤z3≤0.3，0≤z4≤0.45。
2.根据权利要求1所述的储氢合金，其中，0.8≤x1≤0.95，0.05≤x2≤0.2；
优选地，0.9≤x1≤0.95，0.05≤x2≤0.1。
3.根据权利要求1所述的储氢合金，其中，0.5≤y1≤0.8，优选0≤y2≤0.4，优选0≤y3≤0.4，优选0≤y4≤0.4，优选0.01≤y5≤0.2，优选0≤y6≤0.05，优选0≤y7≤0.05；
更优选0.05≤y5≤0.2。
4.根据权利要求1所述的储氢合金，其中，0.1≤z1≤1，优选0.2≤z1≤0.95，优选0≤z2≤0.9，优选0≤z3≤0.2；
优选0.05≤z4≤0.45，更优选0.05≤z4≤0.3。
5.根据权利要求1-4中任意一项所述的储氢合金，其中，所述储氢合金的通式为(Ti0.8V0.2)0.95(Fe1)0.05、(Ti0.8Y0.2)0.95(Mn0.95Ni0.05)0.05、(Ti0.4V0.4Y0.2)0.9(Fe0.05Mn0.95)0.1、(Ti0.4V0.4Y0.2)0.9(Fe0.05Mn0.9Ni0.05)0.1、(Ti0.7Nb0.1Y0.2)0.9(Mn1)0.1、(Ti0.7Nb0.1Y0.2)0.9(Mn0.7Ni0.3)0.1、(Ti0.4Zr0.4Y0.2)0.93(Fe0.2Mn0.7Co0.1)0.07、(Ti0.4Zr0.4Y0.2)0.93(Fe0.2Mn0.7Ni0.1)0.07、(Ti0.4V0.4Zr0.2)0.95(Fe0.6Mn0.2Co0.1Ni0.1)0.05、(Ti0.4V0.35Zr0.2Y0.05)0.95(Fe0.6Mn0.2Co0.1Ni0.1)0.05、(Ti0.88Y0.1Ca0.02)0.95(Fe0.3Mn0.6Co0.1)0.05和(Ti0.88Y0.1Ca0.02)0.95(Fe0.3Mn0.6Ni0.1)0.05中的至少一种；
优选地，所述储氢合金的通式为(Ti0.8Y0.2)0.95(Mn0.95Ni0.05)0.05、(Ti0.4V0.4Y0.2)0.9(Fe0.05Mn0.9Ni0.05)0.1、(Ti0.7Nb0.1Y0.2)0.9(Mn0.7Ni0.3)0.1、(Ti0.4Zr0.4Y0.2)0.93(Fe0.2Mn0.7Ni0.1)0.07、(Ti0.4V0.35Zr0.2Y0.05)0.95(Fe0.6Mn0.2Co0.1Ni0.1)0.05和(Ti0.88Y0.1Ca0.02)0.95(Fe0.3Mn0.6Ni0.1)0.05中的至少一种。
6.权利要求1-5中任意一项所述的固溶体型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：在真空或者惰性气氛下进行，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20-400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中任意一项所述固溶体型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中任意一项所述固溶体型储氢合金。
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