USE OF BIOFUELS

Sources, availability, and processing of biofuels

Introduction

This project is primarily concerned with the thermodynamic, environmental and economic
performance or potential of fuel cells. However, the project teams are interested in these
factors coupled with the feasibility of biofuels for use with fuel cells. It is therefore useful to
explain some details of the types of biofuels which we will consider for use with our fuel cell
"models".

Biofuels are solids, liquids or gases derived from organic materials such as plant life,
industrial or domestic waste including sewage, or agricultural waste (both animal and crop).
These biofuels can be obtained in a number of ways, and can be processed to give refined
fuels, or, in some cases can be used directly. This project is interested in deriving fuels
suitable for use with fuel cells.

The primary focus of our fuel survey is aimed at hydrogen yielding compounds and mixtures
such as "biogas", synthesis gas and methanol. The analysis is broken down into the following
sections -

 Biogas generation from agricultural waste

 Synthesis gas and pyrolysis
 Liquid biofuels
 Sewage biogas
 Landfill gas

The sources of biofuels, their availability and processing requirements for fuel cells are
considered here. The potential for use of biofuels and environmental aspects are considered
in a separate review.

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Agricultural Biogas from Animal Waste and Crops

Biogas Generation Via A Digestor With Stripping or Membrane Purification

As described above the important factor in the use of biogas is the ability to obtain the
maximum practical yield of hydrogen from biogas production. Organic material is introduced
to the digestor where anaerobic digestion or fermentation (that is in the absence of oxygen)
occurs. This produces a "biogas" which consists mainly of methane and carbon dioxide, but
which also contains quantities of hydrogen sulphide and water. In addition to cleaning
increasing the concentration of methane in the biogas mixture it is also necessary to remove
the hydrogen sulphide which is a highly corrosive compound.

In the first of the purification methods, hydrogen sulphide is removed from the biogas by a
process known as chemisorptions usually using iron oxide or zinc oxide. The resultant
product is sulphur, relatively harmless. The use of the carbon dioxide scrubbing column
increases the yield of methane in the resultant biogas.

In the second method, water absorption removes the impurities.

In the third process, membrane separation in the membrane element follows removal of
excess water in the dehydrator. On one side methane gas is yielded, on the other, carbon
dioxide and hydrogen sulphide.

The clean biogas is then stored at pressure for use in the fuel cell.

The results of information searches on the relative yields of biogas of various raw
agricultural biomass materials are shown on the table below.

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 m3 Gas per m3 VS per Culture
BIOMASS CH4Yield/ m3 per Kg VS
day

Cow Manure 0.265 2.21

Pig Manure 0.140 1.3

Kelp 0.281 0.445

Grass 0.184 0.370

Distillery
0.149 2.5
Waste

Energy Crops 0.184 - 0.274 0.7 - 1.0

* Food wastes in this table are generally considered to have a high sugar content

Synthesis Gas and Pyrolysis

Sophisticated techniques allow fast pyrolysis of organic matter (usually wood or other plant
life). With these techniques, the process is carried out at temperatures of 800 - 900 oC. This
leaves only about 10% of the material as solid char and can give up to 60 % of the product
as gas, rich in hydrogen and carbon monoxide. Other organic matter such as rubber and
plastics can be treated in this way. If the temperatures of the process are controlled
appropriately, the composition of the gas can be influenced.

Synthesis gas can be produced in a gasification process, of which there are many. Here, a
solid fuel is reacted with hot steam and air or oxygen (best results are achieved using
oxygen rather than air). If air is used with steam, the resulting gas will contain around 50%
of nitrogen and carbon dioxide, giving relatively low energy content, of around 10% of that
available from methane. If the gasification process uses oxygen rather than air, the energy
content of the resulting gas increases, since there is a negligible amount of nitrogen in the
process.

Liquid Biofuels

Liquid fuels such as methanol and ethanol can be produced from biomass and used to power
fuel cells.

Methanol can be manufactured from synthesis gas produced as described above. Others
have proposed a mixed process where, gas produced from gasification of woody biomass is
further reacted by using steam to shift some CO to CO 2 thus producing sufficient H2 to

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produce methanol. Another proposal was to use natural gas as a co-feedstock. Natural gas
when reformed with steam yields more H 2 than is required for methanol synthesis. It may be
possible to consider mixing biogas from anaerobic digestion as co-feedstock, to improve the
yield of suitable synthesis gas for methanol production. See reference 2

The advantages of methanol over methane include low cost storage for seasonal load
variations and biomass crop yields. The possibility of using direct methanol fuel cells should
not be overlooked.

Ethanol can be produced by a number of fermentation processes using cellulosic biomass as

the feedstock. Such biomass energy crops might be switchgrass, hybrid poplar trees or
sugar cane for example. See reference 2

Sewage Biogas

Biogas can be produced in sewage plants using anaerobic sludge digestion. Usually, the
process is carried out at 30 to 38oC. It is not intended to go into the full detail of anaerobic
digestion processes here; however, the main types are detailed below

 Standard-Rate Digestion. Usually carried out in a single stage where digestion, sludge
thickening and supernatant formation (formation of a clear liquid above a settled
precipitate) occur simultaneously. Untreated sludge is added to the area where
sludge is actively digesting. Heat is applied via external heat exchangers. Gas rises to
the surface and is collected and stored.

 Single-Stage High-Rate Digestion. The difference between this process and standard-
rate process, is that the sludge is added at a much faster rate. There is more
agitation of the sludge by gas recirculation and mechanical mixers, pumping or draft
tube mixers. Again, the sludge is heated to attain optimal digestion rates. Gas may
be stored in the digester with a floating gas holder roof, or drawn off and compressed
for storage.

 Two-Stage Digestion. A high-rate digester is coupled in series with a second digestion

tank. The first tank is used for digestion and is heated and fitted with means of
agitation. The second tank is used for storage and concentration of digested sludge.
Again, gas may be stored in the digester with a floating gas holder roof, or drawn off
and compressed for storage.

PROCESS DESIGN

For sewage plants (***ref from Jorge Here***) the volume of CH 4 produced from a digestor
can be calculated from the following formula

VCH4= (5.62) [ (So- S) (Q) (8.34)-1.42 Px]

Where

VCH4 = the volume of methane gas produced at standard conditions (0oC and 1 atm),
ft3/day

5.62 = theoretical conversion factor for the amount of methane produced from the
complete conversion of 1 pound of BODL to methane and carbon dioxide, ft3BODL
oxidized.

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 Q = flowrate, Mgal/day

So = ultimate BODL in influent, mg/L

S = ultimate BODL in effluent, mg/L

8.34 = conversion factor, lb/Mgal.(mg/L)

Px = net mass of cell tissue produced per day, lb/day

For a complete mix high-rate digester without recycle the mass of biological solids
synthesized daily, Pxj can be estimated using

Px = Y[ (So- S) (Q) (8.34) ] / ( 1 + kdDc )

Where

Y = yield coeeficient, lb/lb

kd = endogenous coefficient, per day

Dc = mean cell-residence time, day

The following table gives some suggested mean cell-residence times for use in the design of
complete-mix digesters

Dc, day ( suggested for

Operating Temperature, oC DcM, day (minimum)
design)

18 11 28

24 8 20

30 6 14

35 4 10

40 4 10

For tank design other factors must be taken into account and incorporated into any sizing
calculations.

Biogas produced from anaerobic digestion of sewage sludge, contains 60 - 70 % CH 4, by

volume. The other constituents are 30 % CO 2, with residual amounts of N2, H2, H2S and water
vapor. As described above for agricultural biogas, some cleaning of the gas will be required.

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GAS PRODUCTION

Total gas production from the breakdown of volatile solids can be estimated as 0.75 - 1.12
m3/kg of volatile solids.

Landfill Gas
The potential to harvest biogas from landfill waste has been harnessed in sites around the
world. In terms of the usefulness of landfill gas for use with fuel cells, there is some scope.

Since a large proportion of municipal solid waste contains biological matter, in the right
conditions anaerobic digestion occurs. This yields gas consisting mainly of CH 4 and CO2 with
between 50 and 60% of the gas being CH 4. The same requirements for cleaning of the gas
prior to reforming, if a fuel is to be used, apply.

In theory, 5-6GJ per tonne of waste is achievable, but practical yields are well below this. The
team did not attempt a case study involving landfill gas.

References
1. Sofer, S S and Zaborsky, O R (editors), Biomas conversion processes for energy and
fuels,Plenum Press
2. Borgwardt, R H,Transportation fuel from cellulosic biomass: a comoparitive
assessment of ethanol and methanol options, Proc Instn Mech Engrs Vol213 Part A
1999
3. Kinoshita, C M; Turn, S Q; Overend, R P; Bain, R L ,Power generation potential of
biomass gasification systems, Journal of Energy Engineering, December 1997
4. Boyle, G ,Renewable energy, power for a sustainable future, Oxford University Press,
1998
5. Palz, W; Coombs, J; Hall, D O,Energy from Biomass, , Proceedings of the International
Conference on Biomass, Held in Venice, Italy 25- 29 March 1985, Elsevier Applied
Science Publishers
6. Bridgewater, A V; Kuester, J L,Research in Thermochemical Biomass Conversion,
International Conference on Research in Thermochemical Biomass Conversion April
1988, Pheonix Arizona