CN111893347A - A2b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
A2b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 PDFInfo
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- CN111893347A CN111893347A CN202010368030.3A CN202010368030A CN111893347A CN 111893347 A CN111893347 A CN 111893347A CN 202010368030 A CN202010368030 A CN 202010368030A CN 111893347 A CN111893347 A CN 111893347A
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- Prior art keywords
- equal
- hydrogen
- ltoreq
- hydrogen storage
- storage alloy
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 220
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 220
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 216
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 98
- 239000000956 alloy Substances 0.000 title claims abstract description 98
- 238000003860 storage Methods 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000013078 crystal Substances 0.000 claims abstract description 5
- 238000003723 Smelting Methods 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 17
- 238000000137 annealing Methods 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 11
- 230000004913 activation Effects 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 230000014509 gene expression Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 229910017279 Ni0.8Co0.2 Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 230000006698 induction Effects 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 13
- 239000005416 organic matter Substances 0.000 abstract description 10
- 238000000746 purification Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000011777 magnesium Substances 0.000 description 33
- 239000007789 gas Substances 0.000 description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 9
- 238000001994 activation Methods 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000003795 desorption Methods 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000006356 dehydrogenation reaction Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010340 TiFe Inorganic materials 0.000 description 1
- 229910010382 TiMn2 Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- -1 cryogenic separation Chemical class 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
本发明涉及储氢合金领域,公开了一种A2B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A2B型晶体结构,A为Mgx1Cax2Tix3Lax4Yx5,B为Cry1Fey2Coy3Niy4Cuy5Moy6;1.29≤x1≤2.09,0≤x2≤0.5,0≤x3≤0.8,0≤x4≤0.5,0.01≤x5≤0.2;0≤y1≤0.3,0≤y2≤0.2,0≤y3≤0.6,0.2≤y4≤1.1,0≤y5≤0.5,0≤y6≤0.15。本发明提供的储氢合金具有较好的氢气提纯能力,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,可以获得高纯度氢气。
Description
技术领域
本发明涉及储氢合金领域,具体涉及A2B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。
目前,工业上对于氢气的纯度要求越来越高,在化工行业中,石油精制需要通过加入氢除去硫,在精制过程中为防止催化剂中毒而要求氢气纯度达到99.99%以上。在电子工业中,多晶硅的制备与外延工艺需要用到氢,对氢的纯度要求极高,即使掺入微量杂质,也会引起半导体的表面特性发生变化;离子管、激光管和氢闸管等各种电子管对填充气体的纯度有更高要求,例如制造显像管时使用的氢气纯度超过99.99%。在玻璃行业中,为了防止浮法玻璃成型设备中熔融的锡液被氧化,需要将锡槽密封,连续不断地送入纯净的氢氮混合气,其中,需要的氢气纯度为99.999%;在能源工业中,质子交换膜燃料电池使用的原料氢中的CO和SO2的含量都低于ppm级。
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。
A2B合金最典型是镁基合金,以重量轻、储量丰富、价格低等诸多优点,成为最有前途的氢储存材料。镁基材料充放氢的热效应比较大,放氢温度一般在300-350℃左右,给使用带来一定的困难,元素取代被认为是改善镁系储氢合金性能的最根本途径。
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。
因此,急需开发一种使用寿命长,氢气纯度可达99.99%以上的氢气纯化技术。
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,氢气纯度有待进一步提高的问题,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的使用寿命,且可以获得纯度在99.99%以上的氢气。
为了实现上述目的,本发明一方面提供一种储氢合金,所述储氢合金具有A2B型晶体结构,其中,A的表达式为Mgx1Cax2Tix3Lax4Yx5,B的表达式为Cry1Fey2Coy3Niy4Cuy5Moy6;
x1、x2、x3、x4、x5、y1、y2、y3、y4、y5、y6分别表示Mg、Ca、Ti、La、Y、Cr、Fe、Co、Ni、Cu、Mo的摩尔数;
其中,x1+x2+x3+x4+x5=1.9-2.1,y1+y2+y3+y4+y5+y6=0.9-1.1;
其中,1.29≤x1≤2.09,0≤x2≤0.5,0≤x3≤0.8,0≤x4≤0.5,0.01≤x5≤0.2;
其中,0≤y1≤0.3,0≤y2≤0.2,0≤y3≤0.6,0.2≤y4≤1.1,0≤y5≤0.5,0≤y6≤0.15。
优选地,0.05≤x5≤0.1。
优选地,0.05≤y1≤0.2。
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具有较好的氢气提纯能力,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,可以获得高纯度氢气。例如,采用本发明实施例7提供的储氢合金,可以得到纯度≥99.99%的氢气,且储氢合金的十次吸氢量可以达到269.45g,且衰减率仅为0.40%。
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。
为了实现上述目的,本发明第一方面提供一种储氢合金,所述储氢合金具有A2B型晶体结构,其中,A的表达式为Mgx1Cax2Tix3Lax4Yx5,B的表达式为Cry1Fey2Coy3Niy4Cuy5Moy6;
x1、x2、x3、x4、x5、y1、y2、y3、y4、y5、y6分别表示Mg、Ca、Ti、La、Y、Cr、Fe、Co、Ni、Cu、Mo的摩尔数;
其中,x1+x2+x3+x4+x5=1.9-2.1,y1+y2+y3+y4+y5+y6=0.9-1.1;
其中,1.29≤x1≤2.09,0≤x2≤0.5,0≤x3≤0.8,0≤x4≤0.5,0.01≤x5≤0.2;
其中,0≤y1≤0.3,0≤y2≤0.2,0≤y3≤0.6,0.2≤y4≤1.1,0≤y5≤0.5,0≤y6≤0.15。
根据本发明,优选地,x2、x3、x4不同时为零。
根据本发明,优选地,1.7≤x1≤2.05,例如x1可以为1.7、1.75、1.8、1.85、1.9、1.95、2、2.05,以及任意两组数之间的任意值。
根据本发明,优选地,0≤x2≤0.2,例如x2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≤x3≤0.5,例如x3可以为0、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≤x4≤0.2,例如x4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≤x5≤0.1,例如x5可以为0.05、0.06、0.07、0.08、0.09、0.1,以及任意两组数之间的任意值。
根据本发明,优选地,y1、y2、y3、y5、y6不同时为零。
根据本发明,优选地,0≤y1≤0.2,更优选地,0.05≤y1≤0.2,例如y1可以为0.05、0.06、0.07、0.08、0.09、0.1、0.11、0.12、0.13、0.14、0.15、0.16、0.17、0.18、0.19、0.2,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,在具有A2B型晶体结构的储氢合金中,在A位点采用Mg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;发明人进一步研究发现,在A位点采用Mg元素和Y元素配合,协同B位点的Ni元素和Cr元素,对含有机物氢气进行提纯效果更显著,且更显著的提高储氢合金的使用寿命。
根据本发明,优选地,0≤y2≤0.1,例如y2可以为0、0.01、0.02、0.03、0.04、0.05、0.06、0.07、0.08、0.09、0.1,以及任意两组数之间的任意值。
根据本发明,优选地,0≤y3≤0.5,例如y3可以为0、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,0.7≤y4≤1.05,例如y4可以为0.7、0.73、0.75、0.77、0.8、0.83、0.85、0.87、0.89、0.91、0.93、0.95、0.97、0.99、1.02、1.05,以及任意两组数之间的任意值。
根据本发明,优选地,0≤y5≤0.4,例如y5可以为0、0.05、0.1、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≤y6≤0.1,例如y6可以为0、0.01、0.02、0.03、0.04、0.05、0.06、0.07、0.08、0.09、0.1,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,所述储氢合金的表达式为Mg1.8Y0.1Ni1、Mg1.8Y0.1Cr0.05Ni1、Mg1.5Ti0.5Y0.05Ni1.1、Mg1.5Ti0.5Y0.05Cr0.1Ni1、Mg2Y0.1Ni0.6Cu0.4、Mg2Y0.1Cr0.05Ni0.6Cu0.4、Mg1.92Y0.08Ni0.95Fe0.05、Mg1.92Y0.08Cr0.2Ni0.75Fe0.05、Mg1.9Y0.1Fe0.1Ni0.8Cu0.1、Mg1.9Y0.1Cr0.1Fe0.1Ni0.7Cu0.1、Mg1.9Y0.1Ni0.8Co0.2、Mg1.9Y0.1Cr0.1Ni0.8Co0.2、Mg1.8Y0.1La0.1Ni0.9Co0.1、Mg1.8Y0.1La0.1Cr0.05Ni0.9Co0.1、Mg1.7Ti0.2Y0.1Ni0.7Co0.32和Mg1.7Ti0.2Y0.1Cr0.05Ni0.7Co0.3中的至少一种;更优选地,所述储氢合金的表达式为Mg1.8Y0.1Cr0.05Ni1、Mg1.5Ti0.5Y0.05Cr0.1Ni1、Mg2Y0.1Cr0.05Ni0.6Cu0.4、Mg1.92Y0.08Cr0.2Ni0.75Fe0.05、Mg1.9Y0.1Cr0.1Fe0.1Ni0.7Cu0.1、Mg1.9Y0.1Cr0.1Ni0.8Co0.2、Mg1.8Y0.1La0.1Cr0.05Ni0.9Co0.1和Mg1.7Ti0.2Y0.1Cr0.05Ni0.7Co0.3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0.6-1bar。
根据本发明,优选地,所述熔炼的时间为0.1-3h,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,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500-900℃,时间为12-360小时;进一步优选地,温度为600-900℃,时间为24-168小时。
所述退火的压力可以为1×10-5-1×10-3Pa。所述退火可以在高真空退火炉中进行。
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。所述冷却优选在真空或者惰性气氛下进行。所述惰性气氛的选择如上所述,在此不再赘述。根据本发明,优选地,在1×10-5-1×10-3Pa条件下,以6-12℃/min(例如为10℃/min)的速率从熔炼温度降温至退火温度。
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)退火得到的物质降温后进行破碎处理以得到10-400目的产品,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3-5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1-8
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;在背景真空1×10-4Pa下以10℃/min的速率降温至退火温度650℃,在该温度下退火48h。在真空下自然冷却至室温。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-C8。储氢合金C1-C8的表达式如表1所示。
实施例9-16
实施例9-16储氢合金的制备条件分别与实施例1-8相同,不同的是,储氢合金的组成,实施例9-16制得的储氢合金C9-C16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
表2
表3
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,在80℃下,用真空泵抽真空5min,然后对储氢罐进行加热,保持储氢合金在0.1MPa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。累计储氢量是指十次吸氢的总量。循环上述吸氢和放氢10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-第十次吸放氢储氢量)/第一次吸放氢储氢量×100%。
表4
通过以上结果可以看出,本发明提供的储氢合金,抗有机物能力强,在氢气中含有机物的情况下,吸氢效率高,具有较高的储氢量,可以获得高纯度(≥99.99)氢气。
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 (11)
1.一种储氢合金,所述储氢合金具有A2B型晶体结构,其中,A的表达式为Mgx1Cax2Tix3Lax4Yx5,B的表达式为Cry1Fey2Coy3Niy4Cuy5Moy6;
x1、x2、x3、x4、x5、y1、y2、y3、y4、y5、y6分别表示Mg、Ca、Ti、La、Y、Cr、Fe、Co、Ni、Cu、Mo的摩尔数;
其中,x1+x2+x3+x4+x5=1.9-2.1,y1+y2+y3+y4+y5+y6=0.9-1.1;
其中,1.29≤x1≤2.09,0≤x2≤0.5,0≤x3≤0.8,0≤x4≤0.5,0.01≤x5≤0.2;
其中,0≤y1≤0.3,0≤y2≤0.2,0≤y3≤0.6,0.2≤y4≤1.1,0≤y5≤0.5,0≤y6≤0.15。
2.根据权利要求1所述的储氢合金,其中,1.7≤x1≤2.05,优选0≤x2≤0.2,优选0≤x3≤0.5,优选0≤x4≤0.2,优选0.05≤x5≤0.1;
优选0≤y1≤0.2,优选0≤y2≤0.1,优选0≤y3≤0.5,优选0.7≤y4≤1.05,优选0≤y5≤0.4,优选0≤y6≤0.1。
3.根据权利要求1所述的储氢合金,其中,0.05≤y1≤0.2。
4.根据权利要求1-3中任意一项所述的储氢合金,其中,所述储氢合金的表达式为Mg1.8Y0.1Ni1、Mg1.8Y0.1Cr0.05Ni1、Mg1.5Ti0.5Y0.05Ni1.1、Mg1.5Ti0.5Y0.05Cr0.1Ni1、Mg2Y0.1Ni0.6Cu0.4、Mg2Y0.1Cr0.05Ni0.6Cu0.4、Mg1.92Y0.08Ni0.95Fe0.05、Mg1.92Y0.08Cr0.2Ni0.75Fe0.05、Mg1.9Y0.1Fe0.1Ni0.8Cu0.1、Mg1.9Y0.1Cr0.1Fe0.1Ni0.7Cu0.1、Mg1.9Y0.1Ni0.8Co0.2、Mg1.9Y0.1Cr0.1Ni0.8Co0.2、Mg1.8Y0.1La0.1Ni0.9Co0.1、Mg1.8Y0.1La0.1Cr0.05Ni0.9Co0.1、Mg1.7Ti0.2Y0.1Ni0.7Co0.32和Mg1.7Ti0.2Y0.1Cr0.05Ni0.7Co0.3中的至少一种;优选地,所述储氢合金的表达式为Mg1.8Y0.1Cr0.05Ni1、Mg1.5Ti0.5Y0.05Cr0.1Ni1、Mg2Y0.1Cr0.05Ni0.6Cu0.4、Mg1.92Y0.08Cr0.2Ni0.75Fe0.05、Mg1.9Y0.1Cr0.1Fe0.1Ni0.7Cu0.1、Mg1.9Y0.1Cr0.1Ni0.8Co0.2、Mg1.8Y0.1La0.1Cr0.05Ni0.9Co0.1和Mg1.7Ti0.2Y0.1Cr0.05Ni0.7Co0.3中的至少一种。
5.权利要求1-4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。
6.根据权利要求5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0.6-1bar。
7.根据权利要求5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500-900℃,时间为12-360小时。
8.根据权利要求5-7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。
9.根据权利要求5-8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。
10.权利要求1-4中任意一项所述储氢合金在储氢过程中的应用。
11.一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1-4中任意一项所述储氢合金。
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