CN111706783A - 一种贮氢合金泡沫板及储氢瓶 - Google Patents
一种贮氢合金泡沫板及储氢瓶 Download PDFInfo
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Abstract
本发明公开了一种贮氢合金泡沫板,其主要成分的质量份数为:超高比表面积活性炭8.55~9.45份,合金粉0.95~1.05份;所述合金粉的质量份数为:镧6.365~7.035份,镍42.75~47.25份,镁3.325~3.675份,铜8.455~9.345份。本发明中贮氢合金泡沫板采用活性炭与合金按照一定比例进行结合制成合金泡沫板,活性炭通过范德华力的结合力束缚氢气分子、合金能够和氢气分子发生化学反应而形成稳定氢化物固定更多的氢原子,从而提高了储氢性能;并且氢化物中的氢原子在镧、镍、镁、铜合金的催化作用下还将产生溢流反应,增强了活性炭对氢分子的吸附作用。本发明具有储量大、耗能小、安全性好、无***危险等特点。
Description
技术领域
本发明涉及一种合金泡沫板,尤其是一种贮氢合金泡沫板及储氢瓶。
背景技术
随着人们对能源和环保意识的增强,越来越清楚地认识到开发清洁能源和有效利用能源的重要性。氢具有资源丰富、可再生的优点,且氢燃烧后的唯一产物是H20,故氢是一种具有光明前景的清洁燃料。氢能高效率地转化为电能,用作燃料电池发电效率可高达80%,是火力发电的2倍多;也可用于氢能飞机,氢能汽车。氢来源非常广泛,可通过电解水,石油、天然气、煤等化石燃料制取,也可由常规燃料醇、烃类制得,也可以由生物质制取(如,细菌制氢、发酵制氢等)。但氢气的储存存在较大的问题,第一,所有元素中氢的重量最轻,在标准状态下,它的密度为0.0899g/L,为水的密度的万分之一。在-252.7℃时,可变成为液体,密度为70g/L,仅为水的十五分之一。第二,作为元素周期表上的第一号元素,氢的原子半径非常小,氢气能穿过大部分肉眼看不到的微孔。不仅如此,在高温、高压下,氢气甚至可以穿过很厚的钢板。三,氢气非常活泼,稳定性极差,泄露后易发生燃烧和***。氢气的***极限:4.0~74.2%(氢气的体积占混合气总质量比)。目前储氢方式主要有物理储氢主要有:高压气态储氢、低温液态储氢、固态合金储氢和多孔材料储氢。对比这几种主要的储氢结果可知,高压气态储氢虽然有简单易行、成本低、冲放速度快等优点。但是,其缺点也很明显,储量小、耗能大、需要耐压容器壁,甚至存在氢气泄露和容器***等不安因素。低温液态储氢具有体积密度高和储氢量大等特点。但液化氢气需要消耗较大的冷能且消耗的能量约为氢气热值的一般,故提高了储氢与放氢的成本。固态合金储氢具有体积储氢密度高、不需要高压容器和隔热容器、安全性好、无***危险、氢气纯度高、操作简便等特点。缺点也很明显,化学储氢存在吸氢温度高、动力学差、可逆性差等缺点。多孔材料储氢是利用多孔材料与氢气通过范德华力进行吸附储氢,但是范德华力的结合力小、氢气存储并不稳定。综上所述,上述四种方案在储氢性能方面仍显不足。
发明内容
本发明要解决的技术问题是提供一种能够提高整体储氢性能的贮氢合金泡沫板;本发明还提供了一种储氢瓶。
为解决上述技术问题,本发明主要成分的质量份数为:超高比表面积活性炭8.55~9.45份,合金粉0.95~1.05份;
所述合金粉的质量份数为:镧6.365~7.035份,镍42.75~47.25份,镁3.325~3.675份,铜8.455~9.345份。
本发明所述超高比表面积活性炭的孔径在0.3nm-1nm,SBET≥2500m2/g。
本发明所述贮氢合金泡沫板为圆板状,在贮氢合金泡沫板上设有通孔;所述通孔包括反应孔、气管孔洞和水管孔洞。
本发明储氢瓶采用上述的贮氢合金泡沫板,还包括有罐体、封头、注水管开关球阀、出水管逆止阀、注水管、出水管、气管、气管球阀和安全阀;所述罐体外上部设有封头;所述罐体内部叠放填充有贮氢合金泡沫板,各个贮氢合金泡沫板的圆形通孔上下对应设置,形成反应通道、气管通道和水管通道;所述水管通道最少为两个,所述注水管穿过一个或一部分水管通道,所述出水管穿过另一个或另外一部分水管通道;所述注水管和出水管在罐体的内下部连通;所述气管穿过气管通道。
上述的储氢瓶,还包括有保持架;所述保持架位于罐体内部并将贮氢合金泡沫板分隔为若干层。
上述的储氢瓶,所述气管的侧壁开有贯通的接触孔。
采用上述技术方案所产生的有益效果在于:本发明泡沫板采用活性炭与合金按照一定比例进行结合制成,活性炭通过范德华力的结合力束缚氢气分子、合金能够和氢气分子发生化学反应而形成稳定氢化物固定更多的氢原子,从而有效地提高了储氢性能;并且氢化物中的氢原子在镧、镍、镁、铜合金的催化作用下还将产生溢流反应,增强了活性炭对氢分子的吸附作用。本发明泡沫板具有单位面积储氢量大、不需要高压容器和隔热容器、安全性好、无***危险等特点。
本发明储氢瓶采用上述泡沫板,且气管、注水管和出水管能够与每一块贮氢合金泡沫板充分接触,贮氢合金泡沫板能够储存尽可能多的氢气,注水管与出水管提供的贮氢合金泡沫板储存氢气的反应条件。本发明储氢瓶能够结合贮氢合金泡沫板对氢气进行释放和吸收,并提供氢气与合金反应结合的条件,辅助提高储氢性能;具有单位面积储氢量大、结构简单、安全可靠等特点。
附图说明
下面结合附图和具体实施方式对本发明作进一步详细的说明。
图1是贮氢合金泡沫板的结构示意图;
图2是储氢瓶的结构示意图;
图3是图2中A部的结构示意图;
图4是储氢***的结构示意图;
图5是储氢***的电原理图。
图中各标号表示为:1、反应孔,2、气管孔洞,3、水管孔洞,4、安全阀,5、出水管逆止阀,6、封头,7、注水管,8、气管,9、出水管,10、注水管开关球阀,11、气管球阀,12、用户端,13、气包,14、制氢设备,15、第二控制模块,16、热水箱,17、冷水箱,18、第一控制模块,19、压力传感器,20、显示器,21、保持架,22、贮氢合金泡沫板,23、接触孔,PLC、控制器。
具体实施方式
本贮氢合金泡沫板的主要成分的质量份数为:超高比表面积活性炭8.55~9.45份,合金粉0.95~1.05份;所述合金粉的质量份数为:镧6.365~7.035份,镍42.75~47.25份,镁3.325~3.675份,铜8.455~9.345份。所述超高比表面积活性炭的孔径在0.3nm-1nm、比表面积SBET≥2500m2/g,合金粉的粒径≤500μm。本贮氢合金泡沫板的制备方法包括混合、硬化工序,各工序工艺如下所述:(1)所述混合工序:将超高比表面积活性炭、镧金属粉末、镍金属粉末、镁金属粉末、铜金属粉末按照配比进行混合;(2)所述硬化工序:在上述粉末中添加粘合剂,混合均匀,然后压制成所需的形状,例如板状,放置、硬化即可。为了防止金属粉末被氧化,在整个制作工序中必须保证真空环境下进行。
本贮氢合金泡沫板中所述活性炭为超微孔活性碳,孔径在0.3nm-1nm。超微孔活性碳具有孔泡和孔泡壁,比重很轻,同时表面积和质量之比极大;此结构的超微孔活性碳吸附面积大,对氢气分子的吸附能力强。图1所示,本贮氢合金泡沫板为方便生产流水作业,做成圆板状,并开有圆形的通孔;所述通孔包括反应孔1、气管孔洞2和水管孔洞3;所述气管孔洞2位于贮氢合金泡沫板的中部;所述水管孔洞3至少有两个,分布设置在贮氢合金泡沫板上,如图1所示为4个;所述反应孔1为若干个,分布设置在贮氢合金泡沫板上,如图1所示为8个。所述水管孔洞3用于穿过注水管、出水管,通过控制所流通的水的温度来控制贮氢合金泡沫板的温度,使得贮氢合金泡沫板22的环境温度由5℃到98℃之间变化。采用上述结构,在最大10Mpa压力条件下,注水管和出水管中流经冷水时,气管孔洞2中的氢气与合金反应结合、存储起来;并且氢化物中的氢原子在镧、镍、镁、铜合金的催化作用下还将产生溢流反应,增强了活性炭对氢分子的吸附作用。所述注水管和出水管中流经热水时,氢气与合金的反应物分解出氢气,氢气释放供用户使用。
图2所示,本储氢瓶,包括贮氢合金泡沫板22、罐体、封头6、注水管开关球阀10、出水管逆止阀5、保持架21、注水管7、出水管9、气管8、气管球阀11和安全阀4。所述罐体为6061铝合金材质且内层镀镍,由于镍有很强的钝化能力,能在表面形成钝化膜抵抗氢气的腐蚀,有效抑制了铝合金的氢脆现象。所述罐体外层缠绕碳纤维和玻璃纤维并浸涂环氧树脂,这样可以为罐体提供抗冲击保护。所述罐体为上部开口的圆筒状,在罐体开口上设有封头6。所述封头封头6与罐体采用法兰结构进行连接,连接处采用O型密封圈密封;这样能够有效保证罐体上部的密封性,使得氢气与外部介质充分隔离。所述罐体内部设有若干个保持架21,保持架21为平板状,且自上而下水平依次设置。所述贮氢合金泡沫板22叠放在各个保持架21的上部,从而将罐体内部填充。所述保持架21为全铝合金材质保持架,将叠放的贮氢合金泡沫板22分隔成若干个单元,可以防止贮氢合金泡沫板22因堆叠过多则造成的粘连,并且能为水管的热传递提供传导的作用。所述贮氢合金泡沫板22在堆叠时,各个通孔上下对应设置;从而形成反应通道、气管通道和水管通道。所述封头6从外向内穿入有一个注水管7、一个出水管9和一个气管8。所述注水管7穿入罐体内部后分支为分注水管道,分注水管道向下穿过一半的水管通道;所述出水管9穿入罐体内部后分支为分出水管道,分出水管道穿过另一半的水管通道;所述分注水管道和分出水管道在罐体的内下部连通;这样就形成水从注水管7进入再从出水管9流出的温控通路。所述气管8向下穿过气管通道,且为开口开口设计;所述气管8的侧壁开有贯通的接触孔23;这样氢气即可通过气管8进入罐体,在气管内流通过程中,氢气通过接触孔23与贮氢合金泡沫板22接触并被吸收;所述氢气从气管8下端开口流出后,向上进入并充满反应通道,能够保证氢气和贮氢合金泡沫板22能够完全接触,以有效地提升贮氢合金泡沫板22吸收氢气的速度。采用上述结构后,贮氢合金泡沫板22水平多层放置的方式能够实现放置最多的贮氢合金泡沫板22,且水管与贮氢合金泡沫板22接触面积尽可能的大,增快了氢气的存储量。所述注水管开关球阀10设置在注水管7的进水端,出水管逆止阀5设置在出水管9的出水端,注水管7和出水管9的所有接头都采用双锥形套密封,能够保证水管的密封性能良好。所述气管8进口安装有气管球阀11和安全阀4;采用双层阀保障,能够满足10MPa工作压力下氢气的气密性,并使得气瓶使用寿命更长。
采用本储氢瓶的储氢***包括所述的储氢瓶,还包括制氢设备14、气包13、第一控制模块18、第二控制模块15、冷水箱17、热水箱16、压力传感器19、用户端12、控制器PLC和显示器20。所述制氢设备14经过气包13后与储氢瓶的气管8连通。所述气包13还与用户端12连通。所述压力传感器19设在储氢瓶内部。所述第一控制模块18一端与出水管9连通,另一端与冷水箱17、热水箱16选择性连通。所述第二控制模块15一端与注水管7连通,另一端与与冷水箱17、热水箱16选择性连通。所述控制器PLC的P1.0接口与压力传感器19连接,P2.2接口与第一控制模块18连接,P2.1接口与第二控制模块15连接,P2.0接口与显示器连接。所述显示屏上有两个按钮:加热按钮和冷却按钮。
采用本储氢瓶的储氢***的工作过程,如下所述:
a、***初始化,压力传感器19检测压力数据,将压力数据输入到控制器PLC,控制器PLC控制显示器20将其显示。若能量为充满,则显示屏20显示“已充满”则执行步骤b。若能量为不足,则显示屏20显示“补充能量”则执行步骤c。
b、切断制氢设备14与气包13的连接,打开气管球阀11,按下加热按钮,第一控制模块18将热水箱16与出水管9连通、第二控制模块15将热水箱16与注水管7连通。贮氢合金泡沫板22受热释放氢气,显示屏20显示“使用中”。
c、切断用户端12与气包13的连接,接通制氢设备14和气包13的连接口,按下降温按钮,第一控制模块18将冷水箱17与出水管9连通、第二控制模块15将冷水箱17与注水管7连通。贮氢合金泡沫板22受冷吸收氢气,显示屏20显示“充气中”。
实施例1-15:本贮氢合金泡沫板的原料配比和制备工艺如下所述。各实施例的具体配比见表1-表3;采用上述储氢***,本贮氢合金泡沫板的储氢能力进行验证;各实施例在压力0.1Mpa、温度10℃条件下的吸收比例,具体见表1-表3。
表1.实施例1-5原料质量配比
表2.实施例6-10原料质量配比
表3.实施例11-15原料质量配比
由实施例1-15分析可以知道,在合金和超高比表面积活性炭比例为0.95:9.45时,合金成分变化的情况下,氢气最高吸收比例高达6.723%。在合金和超高比表面积活性炭比例为1:9时,合金成分变化的情况下,氢气最高吸收比例高达6.725%。在合金和超高比表面积活性炭比例为1.05:8.55时,合金成分变化的情况下,氢气最高吸收比例高达6.727%。实施例中,氢气最高吸收比例为6.727%,而比对照组的最高氢气吸收比例3.8%。据此可以看出,本发明相较于现有技术的储氢方法中储氢能力明显提高。
为了使本发明的技术效果与易于明白了解,以对比试验的方法进行体现。在对试验的试验温度或试验压力控制的情况下,通过测试不同种储氢方案的最佳试验条件,以确定最佳储氢方案的氢气吸收比例。
对比例1-4:超高比表面积活性炭的储氢能力如下所述。
表1.超高比表面积活性炭储氢法中温度变化和氢气吸收比例
对比例 | 试验温度/℃ | 试验压力/Mpa | 吸收比例/wt% |
1 | 10 | 5 | 3.56 |
2 | 20 | 5 | 3.52 |
3 | 30 | 5 | 3.47 |
4 | 40 | 5 | 3.43 |
对表1中数据分析可以知道在试验压力为5Mpa的情况下,试验温度为10℃时,超高比表面积活性炭储氢法中活性炭的氢气吸收比例最高,为3.56%。
对比例5-8:镧镍合金的储氢能力如下所述。
表2.镧镍合金储氢法中温度变化和氢气吸收比例
对比例 | 试验温度/℃ | 试验压力/Mpa | 吸收比例% |
5 | 10 | 0.1 | 1.39 |
6 | 20 | 0.1 | 1.32 |
7 | 30 | 0.1 | 1.26 |
8 | 40 | 0.1 | 1.21 |
对表2中数据分析可以知道在试验压力为0.1Mpa的情况下,试验温度为10℃时,镧镍合金储氢法中镧镍合金的氢气吸收比例最高,为1.39%。
对比例9-12:镁基合金的储氢能力如下所述。
表3.镁基合金储氢法中温度变化和氢气吸收比例
对表3中数据分析可以知道在试验压力为2Mpa的情况下,试验温度为300℃时,镁基合金储氢法中镁基合金的氢气吸收比例最高,为3.8%。
通过分析上述三组对比试验可以知道,超高比表面积活性炭,在试验压力为5Mpa的情况下,试验温度为10℃时,氢气吸收比例最高,为3.56%。镧镍合金在试验压力为0.1Mpa的情况下,试验温度为10℃时,氢气吸收比例最高,为1.39%。镁基合金在试验压力为2Mpa的情况下,试验温度为300℃时,氢气吸收比例最高,为3.8%。可见,现有技术中储氢技术中氢气的最高吸收比例为3.8%,整体储氢性能并不高。
再将上述三组对照组的最佳氢气储量3.8%与采用贮氢合金泡沫板22的储氢***的最佳储氢量6.727%进行对比发现,采用本贮氢合金泡沫板的储氢***的储氢技术远远优于现有技术。
Claims (6)
1.一种贮氢合金泡沫板,其特征在于,其主要成分的质量份数为:超高比表面积活性炭8.55~9.45份,合金粉0.95~1.05份;
所述合金粉的质量份数为:镧6.365~7.035份,镍42.75~47.25份,镁3.325~3.675份,铜8.455~9.345份。
2.根据权利要求1所述的贮氢合金泡沫板,其特征在于:所述超高比表面积活性炭的孔径在0.3nm-1nm,SBET≥2500m2/g。
3.根据权利要求1或2所述的贮氢合金泡沫板,其特征在于:所述贮氢合金泡沫板(22)为圆板状,在贮氢合金泡沫板(22)上设有通孔;所述通孔包括反应孔(1)、气管孔洞(2)和水管孔洞(3)。
4.一种储氢瓶,采用权利要求3所述的贮氢合金泡沫板,其特征在于:还包括有罐体、封头(6)、注水管开关球阀(10)、出水管逆止阀(5)、注水管(7)、出水管(9)、气管(8)、气管球阀(11)和安全阀(4);所述罐体外上部设有封头(6);所述罐体内部叠放填充有贮氢合金泡沫板,各个贮氢合金泡沫板的圆形通孔上下对应设置,形成反应通道、气管通道和水管通道;所述水管通道最少为两个,所述注水管(7)穿过一个或一部分水管通道,所述出水管(7)穿过另一个或另外一部分水管通道;所述注水管(7)和出水管(9)在罐体的内下部连通;所述气管(8)穿过气管通道。
5.根据权利要求4所述的储氢瓶,其特征在于:还包括有保持架(21);所述保持架(21)位于罐体内部并将贮氢合金泡沫板(22)分隔为若干层。
6.根据权利要求4或5所述的储氢瓶,其特征在于:所述气管(8)的侧壁开有贯通的接触孔(23)。
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CN102242861A (zh) * | 2011-05-25 | 2011-11-16 | 北京有色金属研究总院 | 一种大直径储氢合金罐及其制作方法 |
CN105387341A (zh) * | 2015-11-18 | 2016-03-09 | 北京有色金属研究总院 | 一种金属氢化物储氢罐 |
CN106011506A (zh) * | 2016-07-01 | 2016-10-12 | 河南理工大学 | 一种含稀土镁硼的镍氢合金制备设备及方法 |
CN110788329A (zh) * | 2019-11-07 | 2020-02-14 | 江苏集萃安泰创明先进能源材料研究院有限公司 | 含碳复合储氢合金及其制备方法、复合固态储氢罐及储放氢性能测试方法 |
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CN102242861A (zh) * | 2011-05-25 | 2011-11-16 | 北京有色金属研究总院 | 一种大直径储氢合金罐及其制作方法 |
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