CN108607564B - 一种甲醇重整催化剂及其制备和应用 - Google Patents
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Abstract
本发明提供一种甲醇重整催化剂及其制备和应用，所述甲醇重整催化剂采用静电纺丝技术，选择适宜的纺丝聚合物，添加可溶性铜盐及辅助金属盐前驱体，通过合理控制前驱体盐的添加顺序及浓度，得到透明的纺丝溶液，然后通过静电纺丝法得到聚合物/前驱体盐复合纤维，再经高温焙烧，可制备铜系甲醇重整催化剂。本发明提出的方法简单灵活，并且可以通过调变纺丝溶液中不同前驱体盐，及金属盐比例来调变重整催化剂的组成，制备多样铜系重整催化剂。
Description
技术领域
本发明涉及甲醇重整技术领域，特别涉及一种低温甲醇水蒸气重整催化剂的制备方法。
背景技术
质子交换膜燃料电池(PEMFC)是21世纪最有竞争力的高效清洁发电方式之一，但在向商业化迈进的过程中，氢源问题异常突出，氢气供应的设计建设投资巨大，氢气的贮存与运输技术以及氢的现场制备技术等还远落后于PEMFC的发展，氢源问题成为阻碍PEMFC广泛应用与商业化的重要原因之一。
甲醇作为液体燃料，因具有高能量密度，低碳含量，以及运输和贮存等优势成为制氢的理想燃料。甲醇作燃料制取氢气有三种方法：甲醇分解制氢，甲醇水蒸气重整制氢和甲醇催化氧化制氢。由于甲醇水蒸气重整制氢产气中氢气含量高，并且CO含量相对较少，易净化处理，使得甲醇水蒸气重整制氢反应受到广泛关注。
用于甲醇水蒸气重整的催化剂主要有镍系催化剂、铜系催化剂和贵金属催化剂。镍系催化剂稳定性好，适用范围广，但其低温活性不高且选择性差；贵金属催化剂以钯(Pd)系催化剂为主，催化活性高，选择性好，稳定性强；铜系催化剂与贵金属催化剂相比更经济，且选择性和活性也不低，相关研究最多。目前使用的甲醇水蒸气重整制氢催化剂大多采用甲醇合成催化剂，如Cu/ZnO/Al2O3催化剂或在此基础上改性的催化剂，使用温度大都是260～300℃。近年来，研究开发低温甲醇水蒸气重整催化剂得到广泛关注，如果可以将甲醇水蒸气重整的温度降低，则有望将甲醇重整与高温质子交换膜燃料电池相结合实现内部重整。澳大利亚西部大学的Lizhen Gao等人研究报道La2CuO4可以在较低温度(150℃)下实现高效的甲醇转化效率(J.Solid State Chem.,2006,179:2044.,J.Solid State Chem.,2008,181:7-13.)，他们借用单臂碳纳米管(SWNTs)做模板，在SWNTs表面水热合成La2CuO4，再经高温煅烧除去SWNTs，最后得到La2CuO4单晶纳米纤维，在150℃下即可实现100％的甲醇转化率，表明La2CuO4纳米纤维甲醇重整催化剂的优势，但此方法需要制备SWNTs模板，再经水热合成，后续还要除去模板，工序有点复杂。
本发明借助静电纺丝技术，提出一种制备纳米纤维状甲醇重整催化剂的方法。静电纺丝技术是一种简便经济的制备纳米纤维材料的方法，通过选择合适的前驱体盐配比，用适宜的载体聚合物溶液，借助静电纺丝技术，可以得到不同组分的纳米纤维状重整催化剂。
发明内容
本发明采用静电纺丝技术，选择适宜的纺丝聚合物，添加可溶性铜盐及辅助金属盐前躯体，通过合理控制前驱体盐的添加顺序及浓度，得到透明的纺丝溶液，然后通过静电纺丝得到聚合物/前驱体盐复合纤维，再经高温焙烧，可制备铜系甲醇重整催化剂。本发明提出的方法简单灵活，并且可以通过调变纺丝溶液中不同前驱体盐，及金属盐比例来调变重整催化剂的组成，制备多样铜系重整催化剂。
一种甲醇重整催化剂的制备方法，包括以下步骤，
(1)静电纺丝聚合物溶液的配制：所述静电纺丝聚合物于所述溶液中的含量为7～15wt％；
(2)含金属前驱体盐的静电纺丝液的配制：分别配制第一金属前驱体盐溶液和辅助金属前驱体盐溶液；于步骤(1)所述静电纺丝聚合物溶液中，在搅拌条件下匀速加入所述第一金属前驱体盐溶液，加入后持续搅拌至溶液呈透明状；于所得混合溶液中在搅拌条件下匀速加入所述辅助金属前驱体盐溶液，加入后持续搅拌至溶液呈透明状，得含金属前驱体盐的静电纺丝液；
所述第一金属前驱体盐溶液中的溶剂和辅助金属前驱体盐溶液中的溶剂均为步骤(1)所述聚合物溶液中聚合物的良溶剂；
通常来说，在聚合物溶液中加入一种前驱体盐时比较容易，但是加入多种前驱体盐时就有可能因为盐离子与聚合物、盐离子与盐离子间的相互作用而导致溶液配制困难。上述制备方法克服了含两种盐的纺丝溶液配制的困难，
所述第一金属为Cu；所述辅助金属为锰、镧，锆、铈、锌、铝、镍、钼中的任一一种或两种以上。
(3)静电纺丝法制备甲醇重整催化剂：将步骤(2)所得静电纺丝液移入静电纺丝装置中进行静电纺丝，得静电纺丝纤维，对所得静电纺丝纤维进行煅烧处理，得甲醇重整催化剂。
步骤(1)所述聚合物为聚乙烯醇(PVA)、聚氧乙烯(PEO)、聚丙烯酸(PAA)、聚乙烯基吡咯烷酮(PVP)、聚丙烯腈(PAN)、聚偏氟乙烯(PVDF)中的一种；所述聚合物的良溶剂，对于聚乙烯醇(PVA)、聚氧乙烯(PEO)和聚丙烯酸(PAA)所述溶剂为水；对于聚乙烯基吡咯烷酮(PVP)所述溶剂为乙醇、N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMAC)中一种或两种以上的混合溶剂；对聚丙烯腈(PAN)和聚偏氟乙烯(PVDF)所述溶剂为N,N-二甲基乙酰胺(DMAC)、N-甲基吡咯烷酮(NMP)、N,N-二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)中的一种或两种以上的混合溶剂。
步骤(2)所述第一金属前驱体盐溶液和辅助金属前驱体盐溶液中金属盐的质量浓度5-20％。
步骤(2)所述含金属前驱体盐的静电纺丝液中第一金属与辅助金属的原子比为1:1-1:2。
步骤(2)所述含金属前驱体盐的静电纺丝液中聚合物的质量与第一金属的质量比为3:1-5:1。
步骤(3)所述静电纺丝过程为将步骤(2)所述含金属前驱体盐的静电纺丝液移入注射器中，然后固定在静电纺丝的工作台上，注射器针头与接收部件的距离为5～15cm，用注射泵控制纺丝液的进料速度，纺液的进料速度为0.03～1.0mm/min，施加10～30kV的工作电压，将接收部件固定在滚轮上用于收集纤维，用滚轮收集时滚轮旋转速度为100～300rpm；最后将纤维从接收部件上取下。
所述接收部件为铝箔或不锈钢板中的一种。
所述煅烧条件为空气或氧气气氛下，于700-1000℃条件下煅烧1-4h。所述处理过程一方面除去聚合物，另一方面将前驱体盐分解得到相应的金属氧化物。
按照所述方法制备的催化剂为甲醇重整制氢催化剂。
所述催化剂用于甲醇重整燃料电池中。
与现有技术相比，本发明具有方法简单灵活，并且可以通过调变纺丝溶液中不同前驱体盐，及金属盐比例来调变重整催化剂的组成，制备多样纳米纤维状铜系重整催化剂的优点。
附图说明
图1实施例1静电纺丝所得纳米纤维的形貌；
图2实施例1纺丝纳米纤维经高温焙烧后的形貌；
图3实施例1所制备产物的XRD谱图表征；
图4实施例1所制备催化剂在不同温度下的甲醇转化率情况；
图5实施例2所制备催化剂在不同温度下的甲醇转化率情况。
具体实施方式
实施例1
通过静电纺丝法制备CuLa2Ox催化剂。具体制备方法如下：
纺丝溶液的制备：将1g聚乙烯基吡咯烷酮溶解于9g乙醇中得到聚合物溶液；将0.242g硝酸铜(Cu(NO3)2·3H2O)溶于2g乙醇中得蓝色透明溶液、将0.866g硝酸镧(La(NO3)3·6H2O)溶解于5g N,N-二甲基甲酰胺中；先将硝酸铜溶液滴加到聚乙烯吡咯烷酮溶液中，搅拌溶解得到蓝色透明溶液；再将硝酸镧溶液滴加到上述溶液中，溶液中有小珠分散在聚合物溶液中，经过约48h的搅拌，最后得到蓝色透明的纺丝溶液。
将纺丝溶液静置脱泡后移入注射器中，固定在静电纺丝的工作台上，注射器针头距离滚轮的距离为10cm，纺丝溶液的进料速度为0.05mm/min，施加20kV的工作电压，滚轮旋转速度为150rpm。固定在滚轮上的铝箔纸用来收集所得纤维。最后将纤维从铝箔纸上刮下，放入马弗炉内900℃焙烧2h。
图1为静电纺丝所得PVP/Cu(NO3)2/La(NO3)3纳米纤维的形貌；图2为经过高温焙烧后的纤维形貌，可以看出所得纤维经高温焙烧后平均纤维直径平均300nm，；图3为900℃焙烧后产物的XRD谱图，XRD谱图表明所得产物为钙钛矿结构的CuLa2O4和部分CuO及Cu2O。图4为所得纤维用于甲醇重整的性能情况，在约220℃下可实现100％的甲醇转化率。
实施例2
通过静电纺丝法制备CuMnAlOx催化剂。制备方法如下：
将1g聚乙烯基吡咯烷酮溶解于13g乙醇中得聚合物溶液；将0.242g硝酸铜(Cu(NO3)2·3H2O)溶于4g乙醇中得蓝色透明溶液；将0.287g硝酸锰(Mn(NO3)2·6H2O)溶解于2g乙醇和2g N,N-二甲基甲酰胺混合溶剂中得透明溶液；先将硝酸铜溶液滴加到聚乙烯吡咯烷酮溶液中，搅拌溶解得到蓝色透明溶液；再将硝酸锰溶液逐滴加到上述溶液中，边滴加边搅拌，最后继续搅拌得透明纺丝液。随后将纺丝液移入注射器内，固定在静电纺丝的工作台上，注射器距离滚轮的距离为15cm，铝箔纸固定在滚轮表面收集纤维，纺丝溶液的进料速度为0.08mm/min，施加23kV的工作电压，滚轮旋转速度为200rpm。最后将所得纤维在马弗炉内700℃焙烧1h得到CuMnOx催化剂。
图5为实施例2所制备催化剂在不同温度下的甲醇转化率情况，240℃时甲醇转化率可达99％。
Claims (7)
1.一种重整催化剂的应用，其特征在于：所述催化剂用于甲醇重整燃料电池中，所述重整催化剂为甲醇重整制氢催化剂；所述催化剂的制备方法包括以下步骤，
(1) 静电纺丝聚合物溶液的配制：所述静电纺丝聚合物于所述溶液中的含量为7~15wt%；
(2) 含金属前驱体盐的静电纺丝液的配制：分别配制第一金属前驱体盐溶液和辅助金属前驱体盐溶液；于步骤(1)所述静电纺丝聚合物溶液中，在搅拌条件下匀速加入所述第一金属前驱体盐溶液，加入后持续搅拌至溶液呈透明状；于所得混合溶液中在搅拌条件下匀速加入所述辅助金属前驱体盐溶液，加入后持续搅拌至溶液呈透明状，得含金属前驱体盐的静电纺丝液；
所述第一金属前驱体盐溶液中的溶剂和辅助金属前驱体盐溶液中的溶剂均为步骤(1)所述聚合物溶液中聚合物的良溶剂；
所述第一金属为Cu；所述辅助金属为锰、镧，锆、铈、锌、铝、镍、钼中的任一种或两种以上；
(3)静电纺丝法制备甲醇重整催化剂：将步骤(2)所得静电纺丝液移入静电纺丝装置中进行静电纺丝，得静电纺丝纤维，对所得静电纺丝纤维进行煅烧处理，得甲醇重整催化剂。
2.如权利要求1所述重整催化剂的应用，其特征在于：步骤(1)所述聚合物为聚乙烯醇（PVA）、聚氧乙烯（PEO）、聚丙烯酸（PAA）、聚乙烯基吡咯烷酮（PVP）、聚丙烯腈（PAN）、聚偏氟乙烯（PVDF）中的一种；所述聚合物的良溶剂，对于聚乙烯醇（PVA）、聚氧乙烯（PEO）和聚丙烯酸（PAA）所述溶剂为水；对于聚乙烯基吡咯烷酮（PVP）所述溶剂为乙醇、N,N-二甲基甲酰胺（DMF）、N,N-二甲基乙酰胺（DMAC）中一种或两种以上的混合溶剂；对聚丙烯腈（PAN）和聚偏氟乙烯（PVDF）所述溶剂为N,N-二甲基乙酰胺（DMAC）、N-甲基吡咯烷酮（NMP）、N,N-二甲基甲酰胺（DMF）、二甲基亚砜（DMSO）中的一种或两种以上的混合溶剂。
3.如权利要求1所述重整催化剂的应用，其特征在于：步骤(2)所述第一金属前驱体盐溶液和辅助金属前驱体盐溶液中金属盐的质量浓度为5-20%。
4.如权利要求1所述重整催化剂的应用，其特征在于：步骤(2)所述含金属前驱体盐的静电纺丝液中第一金属与辅助金属的原子比为1:1-1:2；
步骤(2)所述含金属前驱体盐的静电纺丝液中聚合物的质量与第一金属的质量比为3:1-5:1。
5.如权利要求1所述重整催化剂的应用，其特征在于：步骤(3)所述静电纺丝过程为将步骤(2)所述含金属前驱体盐的静电纺丝液移入注射器中，然后固定在静电纺丝的工作台上，注射器针头与接收部件的距离为5 ~15cm，用注射泵控制纺丝液的进料速度，纺丝液的进料速度为0.03~1.0 mm/min，施加10 ~30 kV的工作电压，将接收部件固定在滚轮上用于收集纤维，用滚轮收集时滚轮旋转速度为100~300 rpm；最后将纤维从接收部件上取下。
6.如权利要求5所述重整催化剂的应用，其特征在于：所述接收部件为铝箔或不锈钢板中的一种。
7.如权利要求1所述重整催化剂的应用，其特征在于：所述煅烧条件为空气或氧气气氛下，于700-1000℃条件下煅烧1-4 h。
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