Development of Second Generation Technologies:

Processes to Break Down Lignocellulosic Feedstocks

I M Sebastine

Introduction

Transport accounts for 25% of the UK's carbon dioxide (CO2) emissions (1). Low carbon
fuels such as biofuels are expected to play a part in reducing CO2 emissions from the
transport sector. Biofuels are renewable liquid fuels produced from plant or animal
material (biomass) (Figure 1). Plants store their energy as sugar, starch or oil. These
have a high-energy value and can be converted to liquid biofuels. Currently, the two
main types of liquid biofuels are biodiesel, produced from plant oil and bioethanol, from
plant derived sugar or starches, which are known as ‘first generation biofuels’. They are
renewable and have typically lower lifecycle CO2 emissions than petrol or diesel.
However, there are many concerns about the impacts of biofuels. The main issues are
deforestation, biodiversity loss and competition between biofuels and food production.
‘Second generation’ biofuels may offer even lower CO2 emissions, but these are not yet
commercially available (2).

Figure 1. Production pathways to liquid fuels from biomass and, for comparison, from fossil fuels (3)

First generation biofuel technologies

Plant-derived or waste-cooking oil is converted to biodiesel is through a chemical
process called ‘transesterification’. In this process, an alcohol is added which reacts with
the oils. Application of heat and a catalyst induces a chemical reaction which results in

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two products: biodiesel (fatty acid alkyl ester), and glycerine (a by-product) which is
removed, leaving the biodiesel.

Bioethanol

Two key reactions convert biomass to bioethanol:

• Hydrolysis, a chemical reaction that converts the starches in the raw

feedstock to simple sugars. Acids and enzymes are used to catalyze this
reaction.
• Fermentation, a series of chemical reactions that convert sugars to
ethanol. Fermentation is caused by yeast or bacteria which feed on the
sugars. Ethanol and carbon dioxide are produced (4).

After the oils and sugars in the biomass have been converted to biofuel, the by-products
can be burned to produce electricity for the biomass-to-biofuel conversion process. The
residual material from bioethanol production is known as distiller’s dark grain and
solubles (DDGS). It could be used to substitute other solid fuels (e.g. coal), but its main
use is as animal feed.

Second generation biofuel technologies

Second generation is the term used to describe ‘lignocellulosic’ biofuels which are made
from the whole plant, not just from the sugar- or oil-rich components of food crops.
Lignocellulosic biomass is made up of complex sugars, which form the fibrous and
generally inedible portions of plants (1, 5). Biofuels produced from whole plants, can be
derived from a variety of non-food feedstocks including wood, grasses like miscanthus,
purpose grown energy crops such as poplar and willow and biomass wastes from urban,
agricultural, and forestry sources. There are two main technologies to convert whole
plant biomass to liquid biofuels: gasification and chemical conversion.

• Gasification (biomass to liquid conversion)

When biomass is heated with little or no oxygen, it gasifies to a mixture of
carbon monoxide and hydrogen known as syngas. A chemical catalyst is
then added to convert the gas into liquid hydrocarbons (biofuels), a
process known as Fischer-Tropsch (FT) synthesis.

• Chemical (lignocellulosic) conversion /Fermentation

The conversion process begins by pre-treating the biomass to separate it
into its primary components: cellulose, hemicellulose and lignin. Enzymes
are added to the mixture to break down the cellulose into simpler sugars
which are then fermented to create bioethanol.

The production of ethanol from biomass requires the following basic steps: pre-
treatment to hydrolyze the hemicellulose, hydrolysis of cellulose to produce glucose,
fermentation of sugars to ethanol, and ethanol recovery. There are different process

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configurations, both enzyme based and non-enzyme based, that can be used to achieve
the overall goal. In the non-enzyme based approach, acid is used for both hemicellulose
and cellulose hydrolysis, and the mode is separate hydrolysis and fermentation (SHF);
both six-carbon (hexoses, i.e., glucose, mannose, and galactose) and five-carbon
sugars (pentoses, i.e., xylose and arabinose) are fermented to ethanol.

In the enzymatic approach, dilute-acid pretreatment is used to hydrolyze the

hemicellulose portion. The saccharification (hydrolysis) of cellulose to cellobiose and
eventually to glucose is catalyzed by the synergistic action of cellulase and β-
glucosidase enzymes. The mode of operation used is simultaneous saccharification and
co-fermentation (SSCF); co-fermentation refers to the fermentation of both six-carbon
and five-carbon sugars to ethanol.

Organic wastes are potential low cost fermentation substrates for making ethanol. Much
of this waste is crop residues. One such waste material is bagasse, which is the matted
cellulosic fibre residue from sugar cane that has been processed in a sugar mill. It
contains considerable quantities of cellulose, a beta-linked glucose polymer, which is
difficult to break down into glucose. In addition, it contains hemicellulose, which is a
more complex polymer of several sugars including xylose and arabinose. Entwined
around the two sugar polymers is lignin, a polymer that does not contain sugar

Biobutanol has higher energy content than bioethanol, so is more comparable to petrol.
For second generation biofuels, a major obstacle to gasification is that the technology is
not widespread. There are only five Fisher-Tropsch (FT) plants in operation worldwide,
and experience in this process is focused on liquid fuels derived from coal or gas. There
is little experience of gasifying biomass, or of linking it with the FT process.

Research Challenges

• Identifying and developing enzymes capable of efficiently breaking down

the cellulose into simple sugars

• An effective and efficient process for hydrolysis of lignocellulosic biomass

needs to be developed in order to produce second generation biofuels.

• Developing cost effective technology and methods for manufacturing

biobutanol from lignocellulosic biomass.

References:

1. Towards a UK Strategy for Biofuels, DFT, 2004, www.dft.gov.uk

2. Transport Fuels, postnote, Parliamentary Office of Science and Technology, August 2007, Number 293.
3. Biofuel production technologies: status, prospects and implications for trade and development, United
Nations Conference on Trade and Development, Geneva, 2008.
4. Jones, D.T and Woods D.R Acetone-Butanol fermentation revisited, Microbiological Reviews, 1986, 484-524.
5. Angenent, L, Energy biotechnology: beyond the general lignocellulose-to-ethanol pathway, Current Opinion
in Biotechnology, 2007, 18:191–192.
6. A M Henstra, J Sipma, A Rinzema and AJM Stams, Microbiology of synthesis gas fermentation for biofuel
production, Current Opinion in Biotechnology 2007, 18:200–206.