硼氢化钠水解制氢技术研究进展

随着石化能源的日益枯竭,氢能成为解决当前能源危机的一种新能源。制氢的方式多种多样,由于金属氢化物在储氢容量上具有其他材料无法比拟的优势,因此,金属氢化物制氢技术得到了迅速发展。硼氢化钠就是一种典型的金属氢化物,硼氢化钠水解制氢技术作为一种安全、方便的新型制氢技术,已成为当前燃料电池氢源研究中的热点之一。介绍了硼氢化钠制氢原理;综述了硼氢化钠水解制氢技术的优点、影响产氢速率的因素;对硼氢化钠制氢技术的装置进行了举例说明;指出了目前此技术所存在的问题;概述了此技术的应用与发展前景。     

钴-硼/二氧化锆催化剂催化硼氢化钠水解制氢研究

采用浸渍负载-还原法制备了钴-硼/二氧化锆催化剂,研究了催化剂在催化硼氢化钠水解制氢中的性能。研究了催化剂的制备条件（钴与二氧化锆物质的量比、钴与硼氢化钠物质的量比）对其催化性能的影响,并考察了催化剂用量、反应温度、搅拌转速对硼氢化钠水解制氢的影响。结果表明,在钴与二氧化锆物质的量比为0.16:1、钴与硼氢化钠物质的量比为1:5条件下制备的钴-硼/二氧化锆催化剂催化硼氢化钠水解制氢的速率最快。硼氢化钠水解制氢速率随催化剂用量的增加和反应温度的升高而增大,随搅拌转速的增加呈现先增大后减小的趋势。反应动力学计算出钴-硼/二氧化锆催化剂催化硼氢化钠水解对硼氢化钠的浓度属于零级反应。钴-硼/二氧化锆催化剂的硼氢化钠水解反应活化能为43.97 kJ/mol。     

硼氢化钠的制备及水解制氢

NaBH_4的制备已有数种方法的报道,其中以硼酸三甲酯和硼砂为原料的schlesinger法(湿法)和Bayer法(干法)是可以实现工业化的两种重要工艺.而硼氢化钠的水解研究在此之前报道较少,本文研究了NaBH_4的工业制备及常温下水解硼氢化钠制氢的反应及其动力学,探索了水解制氢及应用.     

第四周期过渡金属催化硼氢化钠分解制氢研究

考察了MnSO_4、FeSO_4、CoCl_2、NiCl_2和CuCl等盐原位还原催化硼氢化钠的水解制氢性能,实验确定催化硼氢化钠水解制氢活性高低顺序:CoClNiClFeSO_4CuCl_2MnSO_4,并发现这与第四周期过渡金属d轨道上的电子数有密切关系。硼氢化钠分解产氢速率与FeSO_4、CoCl_2和NiCl_2用量成正比,说明催化硼氢化钠水解产氢的活性中心为过渡金属,且硼氢化钠水解产氢反应对盐的用量为一级反应。实验计算出FeSO_4、CoCl_2和NiCl_2催化硼氢化钠分解制氢反应的活化能分别为52.01、46.33、58.70 kJ/mol,发现硼氢化钠产氢速率与活化能之间没有必然联系。     

自搅拌下CoB/SiO2催化剂催化硼氢化钠水解制氢研究

采用浸渍-化学还原法制备了硼化钴/二氧化硅（CoB/SiO₂）催化剂,并考察了其催化硼氢化钠水解制氢的性能。研究了二氧化硅粒径、硝酸钴与二氧化硅物质的量比、硝酸钴与硼氢化钠物质的量比等条件对催化剂性能的影响,进而考察了催化剂用量、搅拌转速、反应温度等条件对硼氢化钠水解制氢性能的影响。结果表明,在二氧化硅粒径为15 nm、硝酸钴与二氧化硅物质的量比为0.08∶1、硝酸钴与硼氢化钠物质的量比为1∶5条件下,制备的催化剂催化硼氢化钠水解产氢的速率为45.6 mL/（min·g）;因为催化剂粒径很小,伴随硼氢化钠水解产氢产生的动量可以完全消除外扩散速率的影响,搅拌转速对硼氢化钠水解速率的影响很小,硼氢化钠的水解速率随着催化剂用量的增加而增大;随着温度的升高,硼氢化钠的水解速率增大,硼氢化钠水解反应的表观活化能为48.54 kJ/mol,硼氢化钠反应级数为零;催化剂具有良好的重复使用性能和稳定性。     

Mo掺杂的Ni-B非晶态合金的制备及催化硼氢化钠水解制氢

采用化学还原法制备了非晶态Mo-Ni-B催化剂,并用于硼氢化钠水解制氢。通过XRD、SEM、EDX测试证明,Mo-Ni-B为非晶态、均匀的小球状纳米颗粒,平均粒径约30-40nm。硼氢化钠水解制氢性能表明,Mo掺杂后Ni-B的催化活性有所改善,当Mo与Ni的物质的量比为0.04时,该催化剂表现出最好的催化活性。影响因素实验证明,Mo-Ni-B催化Na BH4水解制氢,其产氢速率与体系温度及催化剂用量呈正比,但受硼氢化钠浓度的影响不大。     

硼化钴/石墨烯非晶合金催化剂制备及性能研究

采用载体浸渍、真空干燥和化学还原相结合的方法制备了硼化钴/石墨烯负载型非晶催化剂,系统研究了催化剂在硼氢化钠水解制氢中的催化活性。扫描电镜(SEM)表征表明,硼化钴活性粒子高度分散于石墨烯载体表面,硼化钴纳米粒子的团聚现象得到有效抑制。SEM-EDS(能谱)元素分析表明,硼化钴非晶合金可以在石墨烯表面高效生成,其中钴与硼的原子数比约为2∶1。硼氢化钠水解制氢实验表明,硼化钴/石墨烯负载型非晶催化剂在25℃时催化硼氢化钠水解制氢速率可达252.2 m L/(min·g)。化学反应动力学实验表明,基于硼化钴/石墨烯负载型非晶催化剂催化硼氢化钠水解制氢的反应属于一级反应,其表观活化能约为47.87 k J/mol。     

海绵负载Co-B催化剂催化硼氢化钠水解制氢性能研究

采用浸渍-还原法制备了聚乙烯醇缩甲醛（PVFM）海绵负载的Co-B/PVFM催化剂，考察了硼氢化钠浓度、氢氧化钠浓度及反应温度对其催化硼氢化钠水解制氢性能的影响。结果表明，制氢速率随硼氢化钠的浓度及反应温度的升高而增大，随氢氧化钠浓度的升高呈先增大后减小的趋势，反应活化能为29.02 kJ/mol。在连续式反应器中Co-B/PVFM催化剂催化硼氢化钠水解制氢速率可达12.0 L/min，可为1 kW的燃料电池供应氢气，并且催化活性持续100 min没有发生衰减，表现出极大的实际应用潜力。     

硼氢化钠制氢技术在质子交换膜燃料电池中的研究进展

硼氢化钠储氢量高达10.6%,安全、无爆炸危险,携带和运输方便;供氢系统设备简单,启动速度快,产氢速度可调,因此是一个非常良好的氢载体,是为质子交换膜燃料电池供氢的理想储氢介质。硼氢化钠供氢系统也已逐步应用于质子交换膜燃料电池电源中。介绍了这种制氢方式的几项关键技术：硼氢化钠水解制氢催化剂、硼氢化钠制氢反应器、氢气净化系统等在质子交换膜燃料电池中的研究进展,并指出了今后的研究发展方向。     

CoB催化剂在硼氢化钠-乙醇体系中制氢的应用

采用化学还原法制备了非晶态合金CoB催化剂,研究其在NaBH_4-乙醇复合体系中的催化活性。考察了基于乙醇量(硼氢化钠浓度)、NaOH质量浓度、反应体系温度、醇水体系对CoB催化NaBH_4制氢的影响。结果表明,硼氢化钠产氢速率随着乙醇量(硼氢化钠浓度)的增加呈现出先加快后减缓的变化;NaBH_4产氢速率随碱质量浓度的增加呈现出先增加后减小的变化,且最优碱浓度大约为5%;NaBH_4制氢速率随反应温度增加而快速增加,反应动力学计算显示该体系的表观反应活化能Ea为56.45 kJ/mol;在相同条件下,CoB催化硼氢化钠醇解制氢的产氢速率快于催化硼氢化钠水解制氢的产氢速率。     

Producing hydrogen from sodium borohydride using mesh nickel catalyst

In this study, nickel catalyst in the form of meshes was used in the stationary hydrogen generator with the circulation circuit of reactor to produce hydrogen from sodium borohydride. Based on the tests carried out, optimum parameters of the working process (working solution composition, temperature, pressure) have been determined on sodium borohydride with a capacity on hydrogen of up to 2 nm³/h.     

Mass transfer enhancement factor for chemical absorption of carbon dioxide into sodium metaborate solution

Hydrogen is getting increasing attention as a medium for energy storage, and sodium borohydride is accepted as a suitable carrier for hydrogen. The main product of the process by means of which hydrogen is produced from sodium borohydride is sodium metaborate. Our aim was to find an alternative use for sodium metaborate and specifically investigating the feasibility to use it for carbon dioxide capture from flue gases. The products of this chemical absorption are sodium carbonate, sodium bicarbonate and boric acid, all of which are industrially important chemicals. A bubble column was used in the experiments. Oxygen desorption technique was employed to determine the liquid side physical mass transfer coefficient. Chemical mass transfer coefficient was determined by absorption of carbon dioxide from its mixture with nitrogen into sodium metaborate solution. Enhancement factor was then calculated and a correlation was developed for it.     

Effects of organic acid catalysts on the hydrogen generation from NaBH4

Sodium borohydride has received much attention from fuel cell developers due to its high hydrogen storage capacity. In this study, organic acid solutions such as malic, citric, acetic acids were successfully utilized to accelerate and control hydrogen generation from stabilized sodium borohydride solutions. The generated hydrogen by malic acid was then continuously supplied to a PEMFC single cell. A power density of 168 mW cm⁻² was achieved with a hydrogen flow rate of 0.050 L min⁻¹ that was generated by adding 10 wt% aqueous malic acid to the stabilized sodium borohydride solution at an air flow rate of 0.11 L min⁻¹ without humidification. Further increase of power density to 366 mW cm⁻² is practicable by maintaining a precise hydrogen flow rate of 0.3 L min⁻¹. The current study focuses on the development of an instant hydrogen generation method for micro fuel cell applications. We successfully demonstrated that fast and direct generation of hydrogen could be achieved from stabilized borohydride using inexpensive organic acid solutions rather than expensive metal catalysts and a PEMFC single cell could be operated by generated hydrogen.     

一种硼氢化钠水解制氢的技术路线

硼氢化钠催化水解制氢是一项实用、环保、可行的制氢技术。直接应用固态的硼氢化钠或与催化剂的混合物制氢比使用其溶液制氢更便捷、安全。本文设计了小型制氢反应器,使用NaBH₄和乙酸钴粉末的混合物作初始反应物。研究了初始反应温度、供水速率和NaBH₄与乙酸钴的混合比对产氢特性的影响。实验结果表明,反应区外围使用冷却水时,可将反应温度波动控制在6～8 ℃,这有利于降低氢气流速的峰值和保持相对稳定的氢气流。当催化剂的混合量大于4%时,氢气的转化率可达95%以上。     

硼氢化钠对滑轮用铸钢板化学镀Ni-B合金薄膜性能的影响

在滑轮用铸钢板上化学镀Ni-B合金薄膜,并研究了硼氢化钠的质量浓度对化学镀Ni-B合金薄膜性能的影响。结果表明:适当增加硼氢化钠的质量浓度,有利于增大化学镀Ni-B合金薄膜的厚度及硼的质量分数,从而提高化学镀Ni-B合金薄膜的硬度。当硼氢化钠的质量浓度大于1.2 g/L时,硼氢化钠的水解速率加快及剧烈的析氢反应,导致化学镀Ni-B合金薄膜的厚度及硬度有所降低。当硼氢化钠的质量浓度为1.2 g/L时,化学镀Ni-B合金薄膜表面"胞状"颗粒均匀、致密,摩擦因数和磨损率最低,具有最佳的耐磨性。     

Schlesinger法合成硼氢化钠工艺条件及优化途径

目前工业化合成硼氢化钠的工艺有Schlesinger法和Bayer法,而Schlesinger法是工业化合成硼氢化钠应用最广的工艺,其关键步骤为氢化钠和硼酸三甲酯的合成。本文一方面从氢化钠的合成、硼酸三甲酯的合成及硼氢化钠的合成3个方面详细论述了Schlesinger法合成工艺进展情况;并指出目前方法存在的问题,如采用油液分散金属钠法合成的氢化钠活性差,制约了氢化钠的应用,硼酸三甲酯工业合成过程中过多使用浓硫酸造成环境严重污染。另一方面对Schlesinger法工艺改进提出了几点设想,如企业全流程合成硼氢化钠可节约外购成本和仓储成本;硼酸三甲酯的合成取代浓硫酸的应用,提纯采用盐析的方法均可以减轻环境污染;硼氢化钠水解过程中采用稀液碱溶液代替淡水,可避免硼氢化钠水解,提高产品收率。     

Developing Effective Cobalt Catalysts for Hydrogen-Generating Solid-State NaBH<Subscript>4</Subscript> Composite

Hydrogen-generating solid-state NaBH₄ composite are promising systems for storing and transporting hydrogen intended for use in low-temperature proton-exchange membrane fuel cells. Catalysts are introduced into the composites to ensure the generation of hydrogen at ambient temperatures. In this work, the effect of the synthesis conditions for cobalt catalyst on the gas generation rate is analyzed. It is found that the efficiency of hydrogen generation depends on the nature of the cobalt salt and pH of the aqueous solution of the salt in which the active component precursor is reduced under the action of sodium borohydride because these factors determine the composition, degree of dispersion, and magnetic behavior of the cobalt systems. It is found that the highest rate of gas generation—505 cm³/min per gram of the composite with a hydrogen content of 8.4 wt %—is observed for a sample reduced with sodium borohydride in a hydrochloric acid solution of cobalt chloride with a pH of 1.3. The results can be used to develop effective inexpensive cobalt catalysts for the production of hydrogen from pelletized solid-state NaBH₄ composite.