4.7 Article

Effects of the addition of an organic polymer on the hydrolysis of sodium tetrahydroborate in batch reactors

Journal

INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
Volume 35, Issue 20, Pages 11456-11469

Publisher

PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.ijhydene.2010.07.079

Keywords

Sodium borohydride hydrolysis; Reused Ni-Ru bimetallic catalyst; Hydrogen generation, hydrogen storage, organic polymers

Funding

  1. FCT-Portugal [PTDC/CTM/64191/2006]
  2. Fundação para a Ciência e a Tecnologia [PTDC/CTM/64191/2006] Funding Source: FCT

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An experimental study is presented both on the generation and storage of molecular hydrogen (H-2) by small additions of an organic polymer - carboxymethyl cellulose (CMC) - to sodium borohydride (NaBH4) through the alkaline hydrolysis, in the presence of a powdered nickel-ruthenium based catalyst reused from 274 to 282 times. The experiments were performed at 45 degrees C in two batch reactors with internal volumes of 0.229 L and 0.369 L, made of stainless-steel with bottom conical shape, positioned vertically. The results showed that working at moderate pressures, up to 2.7 MPa, increases slightly the H-2 dissolution in the liquid phase, enhanced by the changing of the polarity of the remained solution inside the reactor: a value of 0.182 for dimensionless H-2 solubility in the liquid phase with 0.25 wt% CMC was found, at 45 degrees C, based on Henry's law. As a consequence, sodium tetrahydroxoborate, NaB(OH)(4) by-product was produced in the presence of CMC additive, showing the absence of crystalline water in its crystal structure (NaB(OH)(4) presents structural water, with boron atoms linked to four hydroxyl groups). This new finding never reported to form at < 50 degrees C, has a positive impact in recyclability costs of NaBO2 back to NaBH4 due to the elimination of two energy consuming steps in the metaborate dehydration kinetics. In fact our system of compressed hydrogen, shows that both H2 generation rates and yields and hydrogen storage capacities can be augmented, the latter to reach approximate to 6 wt%, by adding small amounts of an organic polymer (CMC) to the classic NaBH4 hydrolysis, performed with stoichiometric amount of water. The eventual success of this new route will depend upon developing a advantageous method of converting borates into tetrahydroborate and also finding materials (chemicals) which enhance the solubility of H-2, promoting its reversible storage in the liquid phase. We therefore attempted to show that a less Polar Organic Polymeric Solution (IPOPS) of NaBH4 is a suitable hydrogen carrier for portable and/or niche applications. (C) 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.

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