Alkaline Enhanced Reformation of Biomass

In the EFRI-HyBi system, we utilize Hydrogen in fuel cells to convert chemical

energy into electricity directly with highly efficient conversion rate. Hydrogen
will be gained from reformation of biomass in EFRI-HyBi scheme. However,
various biomasses (e.g. cellulose, cedar wood, rice straw, jute stick, etc)
compose of carbohydrate; thus gasification of biomass may not only
generate hydrogen, but also carbon oxide. Due to the presence of carbon
oxide, the hydrogen generated by the gasification of biomass cannot be
processed directly into fuel cell, the hydrogen at least contains 1 % carbon
monoxide which seriously damages the electrocatalysts at the anode of the
polymer-electrolyte fuel cell (Ishida et al. 2004). Although the PSA (pressure
swing absorption) can lower the concentration of carbon monoxide in the
hydrogen down to less than 20 ppm, the redundancy and cost of additional
processes would make the reformation industrially impractical (Ishida et al.
2006).

Therefore, instead of highly complicacy and cost for removal of CO from the
hydrogen and for the Water Gas Shift reaction, techniques for producing CO-
free hydrogen from biomass are necessitated. Lately, several approaches
have been proposed for producing pure hydrogen from biomass or carbon
materials.

Alkaline Enhanced Reformation is one of the techniques to generate

hydrogen without production of carbon monoxide or carbon dioxide. In the
process of alkaline enhanced reformation, alkaline materials have to be
added into the reformation reactants, water and biomass or biofuels,
therefore changing reaction paths. Besides pure hydrogen generated during
the alkaline enhanced reformation, alkali metal carbonate is also produced
instead of carbon monoxide or carbon dioxide. Alkaline enhanced
reformation also has several additional advantages. The alkaline enhanced
reformation has much lower Gibbs free energy (∆Go) than the conventional
steam reformation (WGS reaction). Thus, the alkaline enhanced reformation
can be conducted at a relatively lower temperature thereforereducing the
operational cost. Moreover, the enthalpy (∆Ho) in the alkaline enhanced
reformation is also much lower than that in the conventional steam
reformation so that heat required for the reaction is much less. (Mays et al.
2006)

Saxena have proven using methane and carbon black to react with sodium
hydroxide in the presence of water vapor; the reaction could produce almost
pure hydrogen and its byproduct solid sodium carbonate over a wide range
of temperatures (373 K-1173 K). The reactions are as follows (Saxena 2003).

CH4 + 2NaOH + H2O = Na2CO3 + 3.5H2

C + 2NaOH+ H2O = Na2CO3 + 1.5H2

In addition to NaOH, several alkali hydroxides (LiOH, KOH, and RbOH) also
have been reported effectively promoting the reformation of carbon into
hydrogen without production of CO or CO2 at temperature > 700 K with
catalysts. (Ishida et al. 2004)

Ishida and his co-workers also successfully developed the reformation of

biomass into hydrogen with alkaline enhanced reformation (e.g. NaOH).
Biomasses, including cellulose, sucrose, glucose, starch, cotton or Japanese
paper, react with NaOH with the existence of water vapor to generate pure
Cox-free hydrogen over a range of 473-623 K. Moreover, some special
catalysts added into the reaction strongly enhanced the production of
hydrogen at the temperature < 573 K (Ishida et al. 2005). The reaction of
cellulose, NaOH, and water vapor is as follows.

C6H10O5+12NaOH+H2O = 6Na2CO3+12H2

The total yield of hydrogen generated by the reaction in the range 473-773 K
was estimated to be 62 % whereas total yield of hydrogen gained from the
reaction can be 100 % in the same range of temperature with specific
catalysts (e.g. Ni, Co, Rh, or Ru) supported on Al2O3 added to the reaction of
cellulose and NaOH (Ishida et al. 2006).

Reference

(1). M. Ishida, M. Toida, T. Shimizu, S. Takenaka, and K. Otsuka, “Formation

of Hydrogen with Cox from Carbon, Water and alkali Hydroxide”, Ind. Eng.
Chem. Res. 2004, 43, 7204-7206.

(2). M. Ishida, S. Takenaka, I. Yamanaka, and K. Otsuka, “Production of Cox-

Free Hydrogen from Biomass and NaOH Mixture: Effect of
Catalysts”, Energy & Fuels 2006, 20, 748-753.

(3). W. Mays, B. Reichman, J. Strebe, and M. Fetcenko, “Reformation Of

Biofuels Using Alkaline Enhancement”, 16th World Hydrogen Energy
Conference.
(4).M. Ishida, K. Otsuka, S. Takenaka and I. Yamanaka, “One-Step production
of CO- and CO2-free hydrogen from biomass”, J. Chem. Tec hnol. &
Biotechnol. 2005, 80, 281-284.