CN112237933A - 制备Co-P-B/泡沫镍催化床用于硼氢化钠水解制氢的方法 - Google Patents
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 80
- 239000001257 hydrogen Substances 0.000 title claims abstract description 80
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000012279 sodium borohydride Substances 0.000 title claims abstract description 51
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- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 4
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- 238000005406 washing Methods 0.000 claims description 4
- 229910021582 Cobalt(II) fluoride Inorganic materials 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910003252 NaBO2 Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt(II) nitrate Inorganic materials [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
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- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
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Abstract
本发明公开了制备Co‑P‑B/泡沫镍催化床用于硼氢化钠水解制氢的方法,其特征在于:包括以下步骤:一:制备Co‑P‑B催化剂浆料;二:喷涂法负载Co‑P‑B催化剂于泡沫镍上:负载前,先将泡沫镍超声清洗,以去除泡沫镍表面的氧化物与杂质;再将通过步骤一制得的Co‑P‑B催化剂浆料均匀喷涂于泡沫镍上,并在真空干燥箱中烘干;三:催化硼氢化钠水解制氢:将负载好Co‑P‑B催化剂的泡沫镍制作成催化床放入反应室中,将反应液硼氢化钠碱性溶液通过输送单元输入反应室中,反应液与催化床接触后,发生水解反应生成H2,反应生成的H2经过气液分离单元分离出;本发明可广泛应用于环保、能源等领域。
Description
技术领域
本发明涉及氢气制备的方法,具体涉及制备Co-P-B/泡沫镍催化床用于硼氢化钠水解制氢的方法。
背景技术
便携式氢燃料电池系统目前已在无人机、车用、机器人、军事、农业等领域得到广泛关注。该系统由储氢部件与氢燃料电池堆两部分组成,目前限制其能量密度的主要瓶颈在于储氢部件。常用的储氢方式主要有压缩氢气瓶、液化氢储存、金属氢化物、化学氢化物等。其中,化学氢化物储氢率高,安全便捷,易于处理与运输,可实现低压在线供氢,具有独特的发展优势。
氢化物中,硼氢化钠(NaBH4)水解制氢是一种极具潜力的在线制氢方式,其水解方程式为:
NaBH4+2H2O→NaBO2+4H2ΔH=-217kJ/mol
常温下,NaBH4水解速率较为缓慢,在溶液中加入NaOH、KOH等碱性稳定剂,可抑制其自水解反应的发生。在pH=14时,NaBH4碱性溶液可稳定储存数月,在催化剂的作用下即可实现快速产氢。采用NaBH4碱性溶液在线水解制氢的优点主要有:1)硼氢化钠质量储氢率高,理论值为10.8wt.%;2)反应所制得氢气纯度高,气相产物仅有氢气;3)反应转化率高,产氢速率快;4)无毒不易燃,可稳定储存,方便运输与携带;5)副产物为偏硼酸钠(NaBO2),性质稳定,无毒不易燃,对环境无害。
催化床在硼氢化钠水解制氢系统中至关重要,是影响制氢速率与NaBH4反应转化率的决定性因素。贵金属催化剂如铂、铑、钌等催化水解性能良好,但储量有限,价格昂贵,从而限制了其规模化生产和应用。非贵金属催化剂如钴、镍、铜及其合金显示出高效的催化活性,价格低廉,是工业应用的最佳选择。其中,以钴为催化活性中心的Co-P-B是一种高效的NaBH4水解制氢催化剂。在连续流反应器中,粉末状催化剂易造成催化剂团聚,管道堵塞,反应之后难以分离回收再利用的问题,因此常将催化剂负载在固态基底上使用。常用的负载基底包括:碳、硅、泡沫镍、铝、离子交换树脂、金属有机骨架等。其中,泡沫镍机械强度高,具有发达的孔隙结构,在催化反应中能保持良好的热化学稳定性,是催化NaBH4水解制氢的良好基底。
发明内容
本发明所要解决的技术问题在于提供一种制备Co-P-B/泡沫镍催化床用于硼氢化钠水解制氢的方法。
本发明的技术方案是,一种制备Co-P-B/泡沫镍催化床用于硼氢化钠水解制氢的方法,其特征在于:包括以下步骤:
步骤一:制备Co-P-B催化剂浆料,具体为:
(1)、配制Co2+盐与H2PO2 -盐的混合溶液,记为前驱体溶液;
(2)、配制硼氢化钠碱性溶液;
(3)、将步骤(2)配制的碱性溶液缓慢加入到前驱体溶液中,剧烈搅拌,获得含有Co-P-B催化剂颗粒的悬浊液;
(4)待反应完全后,将悬浊液静置至室温,并利用离心机将Co-P-B催化剂颗粒从悬浊液中分离,再将Co-P-B催化剂颗粒洗涤若干次,完成Co-P-B催化剂颗粒的制备;
(5)、将洗涤好的Co-P-B催化剂颗粒加入到一定体积的含有粘结剂的浆料中,搅拌均匀后,超声振荡,获得Co-P-B催化剂浆料;
步骤二:喷涂法负载Co-P-B催化剂于泡沫镍上:
负载前,先将泡沫镍超声清洗,以去除泡沫镍表面的氧化物与杂质;再将通过步骤一制得的Co-P-B催化剂浆料均匀喷涂于泡沫镍上,并在真空干燥箱中烘干;
步骤三:催化硼氢化钠水解制氢:
将负载好Co-P-B催化剂的泡沫镍制作成催化床放入反应室中,将硼氢化钠碱性溶液通过输送单元输入反应室中,反应液硼氢化钠碱性溶液与催化床接触后,发生NaBH4水解反应生成H2,反应生成的H2经过气液分离单元分离出。
根据本发明所述的制备Co-P-B/泡沫镍催化床用于硼氢化钠水解制氢的方法的优选方案,所述Co2+盐可选用CoCl2、Co(CH3COO)2、CoSO4、CoF2或者Co(NO3)2;所述H2PO2 -盐可选用NaH2PO2或者KH2PO2。
根据本发明所述的制备Co-P-B/泡沫镍催化床用于硼氢化钠水解制氢的方法的优选方案,粘结剂选用Nafion膜溶液、PTFE溶液或者丁苯橡胶。
根据本发明所述的制备Co-P-B/泡沫镍催化床用于硼氢化钠水解制氢的方法的优选方案,其特征在于:Co-P-B催化剂中Co、P、B原子比为1:0.5~1.2:1.5~3.5。
本发明所述的制备Co-P-B/泡沫镍催化床用于硼氢化钠水解制氢的方法的有益效果是:本发明提出采用还原-喷涂的方法制备高效的Co-P-B/泡沫镍催化床,该方法安全简便,适用于工业大规模生产应用,该催化床可直接应用于NaBH4水解制氢系统,在线供氢给燃料电池使用,满足燃料电池在不同功率条件下的供氢需求,拓宽燃料电池的应用场景,对硼氢化钠在线水解制氢燃料电池系统的推广应用具有较重要的应用价值,可广泛应用于无人机、车用、机器人、军事、农业等领域。
附图说明
图1是采用本发明制备的催化床NaBH4水解产氢速率与反应室温度随时间的变化规律图。
图2是在不同Co-P-B催化剂载量下产氢流量的变化规律图。
图3是在不同进液速度下产氢流量的变化规律图。
图4是在不同圆柱型催化床长度下产氢流量的变化规律图。
具体实施方式
实施例1,一种制备Co-P-B/泡沫镍催化床用于硼氢化钠水解制氢的方法,包括以下步骤:
步骤一:化学还原法制备Co-P-B催化剂浆料。具体为:
(1)、配制Co2+盐与H2PO2 -盐的混合溶液,记为前驱体溶液;Co2+盐可选用CoCl2、Co(CH3COO)2、CoSO4、CoF2、Co(NO3)2等,H2PO2 -盐可选用NaH2PO2、KH2PO2等。
(2)、配制NaBH4碱性溶液;碱性稳定剂可选用NaOH、KOH等,质量分数为1-15%。
(3)、将步骤(2)配制的NaBH4碱性溶液缓慢加入到前驱体溶液中,剧烈搅拌,获得含有黑色Co-P-B催化剂颗粒的悬浊液;伴随产生大量的气泡。催化剂Co、P、B原子比为1:0.5~1.2:1.5~3.5。
(4)待反应完全后,将悬浊液静置至室温,并利用离心机将Co-P-B催化剂颗粒从悬浊液中分离,再将Co-P-B催化剂颗粒用去离子水、无水乙醇洗涤若干次,完成Co-P-B催化剂颗粒的制备;
(5)、将洗涤好的催化剂颗粒取出,加入到一定体积的去离子水与粘结剂的混合浆料中。搅拌均匀后,超声振荡15~30min。粘结剂可选用Nafion膜溶液、PTFE溶液、丁苯橡胶等,优选5%Nafion膜溶液。混合浆料中去离子水与粘结剂溶液的体积比为100:0.5~2。
步骤二:喷涂法负载Co-P-B催化剂于泡沫镍上。负载前,先将泡沫镍依次使用1wt%的稀HCl溶液与无水乙醇超声清洗15min,再用去离子水冲洗若干次,以去除泡沫镍表面的氧化物与杂质。随后,用喷枪将通过步骤一制得的Co-P-B催化剂浆料均匀喷涂于泡沫镍上,并在真空干燥箱中烘干。催化剂载量通过差重法获得。所述的催化剂载量为3~7mg/cm2。
步骤三:催化NaBH4水解制氢。负载好催化剂的片状泡沫镍即可用于固定床连续流式装置中。本发明以圆柱型反应室为例,但不局限于此。将泡沫镍沿长度方向卷曲成一定直径的圆柱型催化床后,放入反应室中。将NaBH4碱性溶液通过输送单元,例如蠕动泵,将NaBH4碱性溶液输入反应室中,进液速度可调控。反应液NaBH4碱性溶液与催化床接触后,随即发生NaBH4水解反应。反应生成的NaBO2和H2经过气液分离单元,分离出的H2经过洗气和干燥后,即可通入氢燃料电堆中使用。
实施实例2:
步骤一:化学还原法制备Co-P-B催化剂浆料。配制1mol/L CoCl2与0.8mol/LNaH2PO2的混合溶液共100mL,记为前驱体溶液A;2mol/L NaBH4与0.5mol/L NaOH混合溶液共100mL,记为溶液B。将溶液B缓慢加入到前驱体溶液A中并剧烈搅拌。溶液中迅速生成黑色的Co-P-B催化剂颗粒,伴随产生大量的气泡。待反应完全后,将悬浊液静置至室温并利用离心机将Co-P-B催化剂颗粒从悬浊液中分离。随后将催化剂用去离子水、无水乙醇洗涤若干次。将洗涤好的催化剂颗粒取出,加入100mL去离子水,1mL5%的Nafion膜溶液,搅拌均匀后,超声振荡20min后进行催化剂的负载。
步骤二:喷涂法负载Co-P-B催化剂于泡沫镍上。首先将泡沫镍裁剪为10×20cm2大小,并依次使用1wt%的稀HCl溶液与无水乙醇超声清洗15min,再用去离子水冲洗若干次,以去除泡沫镍表面的氧化物与杂质。随后,用喷枪将上述制得的Co-P-B催化剂浆料均匀喷涂于泡沫镍上,并在真空干燥箱中烘干。催化剂载量通过差重法获得,控制为6.0±0.2mg/cm2。负载好催化剂的片状泡沫镍沿长度方向卷曲成直径25mm左右,长度10cm的圆柱型催化床。
步骤三:催化NaBH4水解制氢。将制备的圆柱型Co-P-B/泡沫镍催化床放入内径26mm的反应室中,测试其对NaBH4水解制氢的催化性能。将NaBH4碱性溶液(20wt%NaBH4,5wt%NaOH)通过蠕动泵泵入反应室中,进液速度为4mL/min,反应液与催化床接触,随即发生NaBH4水解反应。反应生成的NaBO2和H2经过一个气液分离单元,分离出的H2经过洗气和干燥后,通过气体质量流量计测量流量。通过数据采集器每隔两秒采集一次流量计测得的流量信号与反应室外壁面热电偶测得的温度信号,再传输到电脑中进行数据的处理。其产氢速率(25℃,101kPa)与反应室温度随时间的变化规律如图1所示。
实施实例3:
图2显示了不同Co-P-B催化剂载量下平均产氢流量的变化规律。随着Co-P-B载量的增加,产氢流量增加,越来越接近理论值,即催化床的催化性能越好,使得NaBH4水解反应更为完全。当Co-P-B载量为6mg/cm2时,催化效率相较于理论值只相差0.044L/min,达到理论产氢流量的96%。
实施实例4:
图3显示了不同进液速度与平均产氢速率的相互关系。从图中可以看出,产氢速率与进液速度基本呈现正相关关系,即使在高进液速度下(4mL/min),该催化床也可达到接近于理论值的产氢速率,能很好满足不同产氢速率的需求。典型的100W质子交换膜氢空燃料电池堆消耗氢气的速率为1.55L/min(25℃,101kPa),因此,在4mL/min进液速度下的产氢流量(2.14L/min)可满足电堆138W功率下的供氢需求。同时,从图中还可以得知,在实际NaBH4水解制氢系统中,只需调节泵的功率,控制进液速度,即可获得不同的产氢流量,使其与氢燃料电堆的功率相匹配。
实施实例5:
图4显示了不同圆柱型催化床长度与平均产氢速率的相互关系。从图中可以看出,产氢速率随催化床长度增加而增加,越来越接近于理论值。同时,从图中还可以推断出,NaBH4水解反应主要发生在催化床前端部分,10cm长度催化床下,在中段6cm处,NaBH4水解转换率即可达到90%以上。
本发明的原理如下:
以钴为催化活性中心的Co-P-B是一种高效的NaBH4水解制氢催化剂。在连续流反应器中,粉末状催化剂易造成催化剂团聚,管道堵塞,反应之后难以分离回收再利用的问题,因此常将催化剂负载在固态基底上使用。泡沫镍机械强度高,具有发达的孔隙结构,在催化反应中能保持良好的热化学稳定性,是一种催化NaBH4水解制氢的良好基底。本发明所提出的还原-喷涂法安全简便,经济实用,适合工业上机械大规模制备。由此方法制备的Co-P-B/泡沫镍催化床催化性能极好,NaBH4的反应转化率可达到96%以上,产氢速率接近理论产氢速率,实现NaBH4的充分利用,减小储氢成本。该催化床制备方法在NaBH4在线水解制氢燃料电池系统未来大规模实际应用中体现出较大的优势,具有较大的应用潜力。
本发明与现有技术相比具有如下优势:
1)本发明采用还原-喷涂法制备Co-P-B/泡沫镍催化床,安全简便,经济实用,适合工业上大规模运用;
2)本发明制备的催化床催化性能极好,可实现接近理论值的NaBH4反应转换率及水解产氢速率,能充分利用NaBH4,降低储氢成本;
3)采用本催化床的NaBH4在线水解制氢燃料电池系统具有响应速度快、能量密度高等特点。
以上实施例仅用以说明本发明的技术方案而非限制,尽管参照较佳实施例对本发明进行了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的宗旨和范围,其均应涵盖在本发明的权利要求范围当中。
Claims (4)
1.一种制备Co-P-B/泡沫镍催化床用于硼氢化钠水解制氢的方法,其特征在于:包括以下步骤:
步骤一:制备Co-P-B催化剂浆料,具体为:
(1)、配制Co2+盐与H2PO2 -盐的混合溶液,记为前驱体溶液;
(2)、配制NaBH4碱性溶液;
(3)、将步骤(2)配制的碱性溶液缓慢加入到前驱体溶液中,剧烈搅拌,获得含有Co-P-B催化剂颗粒的悬浊液;
(4)、待反应完全后,将悬浊液静置至室温,并利用离心机将Co-P-B催化剂颗粒从悬浊液中分离,再将Co-P-B催化剂颗粒洗涤若干次,完成Co-P-B催化剂颗粒的制备;
(5)、将洗涤好的Co-P-B催化剂颗粒加入到一定体积的含有粘结剂的浆料中,搅拌均匀后,超声振荡,获得Co-P-B催化剂浆料;
步骤二:喷涂法负载Co-P-B催化剂于泡沫镍上:
负载前,先将泡沫镍超声清洗,以去除泡沫镍表面的氧化物与杂质;再将通过步骤一制得的Co-P-B催化剂浆料均匀喷涂于泡沫镍上,并在干燥箱中烘干;
步骤三:催化NaBH4水解制氢:
将负载好Co-P-B催化剂的泡沫镍制作成催化床放入反应室中,将NaBH4碱性溶液通过输送单元输入反应室中,反应液与催化床接触后,发生NaBH4水解反应生成H2,反应生成的H2经过气液分离单元分离出。
2.根据权利要求1所述的制备Co-P-B/泡沫镍催化床用于硼氢化钠水解制氢的方法,其特征在于:所述Co2+盐可选用CoCl2、Co(CH3COO)2、CoSO4、CoF2或者Co(NO3)2;所述H2PO2 -盐可选用NaH2PO2或者KH2PO2。
3.根据权利要求1所述的制备Co-P-B/泡沫镍催化床用于硼氢化钠水解制氢的方法,其特征在于:粘结剂选用Nafion膜溶液、PTFE溶液或者丁苯橡胶。
4.根据权利要求1所述的制备Co-P-B/泡沫镍催化床用于硼氢化钠水解制氢的方法,其特征在于:Co-P-B催化剂中Co、P、B原子比为1:0.5~1.2:1.5~3.5。
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