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Conversion of Biomass to Methanol and Ethanol

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DOI: 10.1007/978-3-030-29069-6_4

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Conversion of Biomass to Methanol
and Ethanol
G. Karthiga Devi, S. Chozhavendhan, J. Jayamuthunagai, B. Bharathiraja
and R. Praveen kumar

Abstract The rapid exhaustion of fossil fuels and greenhouse effect leads to work
on alternate energy and fuel source. In which, ethanol and methanol are widely dis-
cussed as an alternate for fuels over the decade. Fuels derived from the microbial
biomass are one of the most promising renewable energy resources when compared to
the conventional fuels from the petroleum reserves, which create excessive green gas
emissions. The microbes are ubiquitous and many microbes are capable of convert-
ing the carbon source into primary metabolites, especially alcohols. Waste material
generated from the industries like biodiesel, cassava, paper and pulp industries are
rich in carbon and cellulose, which can be utilized by the microbes as carbon and
energy source for the production of ethanol and methanol.

Keywords Microbes · Biofuel · Genetic engineering

1 Introduction

In recent times, there is an urge in the global ecosystem to find an alternative renew-
able source because of the negative impact of fossil fuels on the environment, par-
ticularly greenhouse gas emissions. Biomass is one such potential renewable source
obtained from plants, animals and microorganisms which are non-fossilized as well as
biodegradable. The fuels can be generated from the decomposition of above organic

G. K. Devi (B)
Saveetha School of Engineering, Chennai, Tamil Nadu, India
e-mail: devigk19@gmail.com
S. Chozhavendhan
Vivekanandha College of Engineering for Women, Tiruchengode, Chennai, India
J. Jayamuthunagai
Centre for Biotechnology, Anna University, Chennai, India
B. Bharathiraja
Vel Tech High Tech Dr Rangarajan Dr Sakunthala Engineering College Avadi, Chennai, India
R. Praveen kumar
Arunai Engineering College, Tiruvannamalai, India

© Springer Nature Switzerland AG 2019 61

R. Pogaku (ed.), Horizons in Bioprocess Engineering,
https://doi.org/10.1007/978-3-030-29069-6_4
62 G. K. Devi et al.

materials but they have low energy densities when compared to fossil fuels. How-
ever, this kind of fuel production from the woods, especially from wastes of animals,
plants and food processing industries has attracted attention due to its sustainability
and low-cost feedstock.
Varieties of methods are possible for the production of energy from biomass is
possible through biochemical conversions. Biomass-based fuels possess many advan-
tages such as (1) renewable resource that could be sustainable for future use (2) lessen
the concentration of greenhouse gases in the environment thereby replacing fossil-
based fuels, (3) represented as a carbon cycle in combustion process, (4) Possess
significant economic potential when compared to the existing high price fossil fuels
(IEA 2004).
Ethanol and Methanol possess increasing demand over fossil fuels because it
plays a significant role in the large scale transportation. There is no other fuel that
can match ethanol and methanol produced using biomass in meeting the economic
requirements. The advancements has made in the production technology in order to
reduce the cost of production primarily for its use as an alternative fuel.

2 Types of Biomass

Biomass are categorized into various types such as (1) Forest products (wood, logging
residues, trees, shrubs and wood residues, sawdust, bark), (2) Bio-renewable wastes
(agricultural wastes, crop residues, mill wood wastes, urban wood wastes, urban
organic wastes), (3) Energy crops (short-rotation woody crops, herbaceous woody
crops, grasses, starch crops, sugar crops, forage crops, oilseed crops, switchgrass,
miscanthus), (4) Aquatic plants (algae, water weed, water hyacinth, reed and rushes),
(5) Food crops (grains, oil crops, Sugar crops, Sugar cane, sugar beets, molasses,
sorghum), (6) Landfill (hazardous waste, nonhazardous waste, inert waste, liquid
waste), (7) Organic wastes (municipal solid waste, industrial organic wastes, munic-
ipal sewage and sludge), (8) Algae (prokaryotic algae, eukaryotic algae, kelps), (9)
Mosses (bryophyta, polytrichales), (10) Lichens (crustose lichens, foliose lichens,
fruticose lichens) (Speight 2010).

3 Classification of Biofuels Based on Biomass

Biofuels can be classified into three categories based on the availability of sources
and types of production processes. The possible products obtained from biomass
include biodiesel, ethanol, butanol, methane, hydrocarbons and natural oils, which
can be further processed into any number of desirable fuels (Pena 2007). Biofules are
classified based on their standards by the European committee for standardization
and are labelled as EN standards (Table 1).
Conversion of Biomass to Methanol and Ethanol 63

Table 1 Comparison of different types of fuels

Feedstock Conditions Biofuel production References
First-generation fuels
Corn hydrolysis/fermentation 3,800 L/ha Lin and Tanaka (2006)
Sugarcane fermentation 7,200 L/ha
Sugar beet hydrolysis/fermentation 7,900 L/ha
Wheat hydrolysis/fermentation 1700 L/ha
Cassava hydrolysis/fermentation 137 L/ha
Second-generation fuels
Reed canary grass Gasification 0.3–1.2 toe/ton Singh et al. (2010)
Jatropha Gasification 2.0–3.0 toe/ton Koh and Mohd. Ghazi
(2011)
Miscanthus S Biochemical 0.8–6.9 toe/ton Cadoux et al. (2012)
conversion
Switchgrass Pyrolysis 0.7–3.0 toe/ton Heaton et al. (2004)
Third-generation fuels
Spirulinaplatensis Reaction temperature 60 g/kg lipid Nautiyal et al. (2014)
55 °C, 60% catalyst
concentration, 1:4
algae biomass to
methanol ratio,
450 rpm stirring
intensity
Nannochloropsissp Oil extraction with 99 g/kg lipid Susilaningsih et al.
n-hexane, acidic (2009)
transesterification
Scenedesmus sp. Alkaline (NaOH), 321.06 g/kg lipid Kim et al. (2014)
temperature of 70 °C
Nannochloropsissalina Acidic (H2SO4) 282.23 g/kg lipid Muthukumar et al.
catalyst, temperature of (2012)
70 °C
Nicotianatabacum cv. Glucocorticoid gene 1.6 times the higher Pankaj S. Kuhar (2014)
Xanthi responsible for growth biomass when
has been activated by compared to control
means of which can be
Agrobacterium- accounted for fuel
mediated production
transformation
Manipulation of lignin Downregulation by 45% reduction in total Hu et al. (1999)
biosynthetic pathway antisense constructs of lignin content and a
in woody plants 4CL in transgenic P. 15% increase in
tremuloides resulted in cellulose
a
Overexpression of Up-regulation of genes Increase in biomass Eriksson et al. (2000)
Gibberellin 20-oxidase, involved in the productivity and
agibberellin thickening of the proportionally,
biosynthesis gene in secondary cell wall polysaccharide content
growing trees with during plant
increased stem biomass development
and xylem fibres
64 G. K. Devi et al.

3.1 First-Generation Fuels

First-generation Biofuel production mainly involves the use of agricultural crops rich
in sucrose such as sugarcane, sugar beet, sorghum, whey, molasses, starchy grain
feedstocks and root crops as source (Lin and Tanaka 2006). Sugar crops contain high
amount of sugar and they can be extracted by milling process for the conversion into
ethanol by means of fermentation. Starch grain involves enzymatic hydrolysis with
the help of microorganisms for the conversion into sugar molecules (Persson et al.
1991). This involves the use of cellulose hydrolyzing enzymes such asendo-β-1,4-
glucanases, cellobiohydrolases and β-glucosidases. First-generation fuel possesses
many advantages such as simple production strategies, high availability of famil-
iar feedstocks, easily scalable production capacities and fungibile with petroleum-
derived fuels.

3.2 Second-Generation Fuels

Polysacharides containing feedstocks such as wood, straw and grasses occupy a major
place in the production of second-generation fuels (REN21 2013). Lignocellulosic
biomass includes woody materials, straws, crop residues and agricultural wastes,
which come under this category. This requires pretreatment for the conversion into
simple sugar molecules. Several unit operations involved in the pretreatment pro-
cesses varying from physical (milling, ultrasound and mechanical grinding), chemi-
cal (acid/alkali treatment) to biological (enzyme addition). Once the lignin has been
removed, it aids hydrolysis of the biomass (Sims et al. 2010).

3.3 Third-Generation Fuels

Third-generation biofuels are obtained from algal biomass and other microbes
(Nigam and Singh 2011). This is the rapidly growing feedstock among all the organ-
isms, which results in excellent production of oils. This undergone thermochemical
conversion to diesel requires extreme downstream operations (pyrolysis, gasification,
liquefaction and combustion), especially dewatering procedures.

3.4 Fourth-Generation Fuels

Fourth-generation fuels come under third-generation procedure or the exten-

sion of third-generation fuels produced using microorganisms. This mainly
Conversion of Biomass to Methanol and Ethanol 65

involves the application of Genetic engineering techniques in which the modifi-

cation/transformation of genes to alter the cellular metabolism so that it enhances
the hydrocarbon yield for the production of biofuel. Fourth-generation biofuels not
only captures and stores carbon dioxide from the atmosphere; it also reduces carbon
dioxide emission by replacing fossil fuels. By using this technique, we can reduce
the emission of poisonous gases. This requires high investment but it is economical
in long term.

3.5 Parameters Involved in the Production of Biofuels

Various physical parameters of biomass are known to influence the production of

biofuel using biomass as source such as moisture content, particle size, ash content
and toxicity highly influences the quality of biofuel. The technologies used for bio-
fuel production chosen based on the amount moisture content present in the biomass.
Bioconversion processes are generally applied for the biomass rich in moisture con-
tent while Thermoconversion processes are applied for the biomass less than 20%
moisture content. Other factors influencing the production are their pH, temperature,
their tolerance towards the inhibitory compounds (Zabed et al. 2014).

4 Technologies Involved in Biofuel Production

Biomass can be converted to fuel, which offers an alternative approach to generate

energy for transportation. Biomass produces a variety of solid, liquid and gaseous
fuels using biological as well as thermal technologies. Solid biofuels are produced
using charcoal and dried biomass materials. Liquid biofuels are produced by either
physical/chemical/biological processing of the biomass materials. Gaseous biofuels
are produced through anaerobic digestion or gasification.

4.1 Acid Hydrolysis

This method involves the use of concentrated sulphuric acid for the cellulose hydrol-
ysis, which acts as power catalyst but it is highly corrosive in nature (Jeffries and
Jin 2000). Enzymatic hydrolysis seems better than acid hydrolysis but it requires
expensive chemicals for the pretreatment procedures (Bharathiraja et al. 2014).
66 G. K. Devi et al.

4.2 Anaerobic Digestion

This involves the decomposition of organic materials to gaseous fuel by the action
of bacteria in an oxygen-free environment (Chynoweth et al. 2001). The process
involves four steps, namely hydrolysis and fermentation, transitional acetogenic
dehydrogenation and methanogenesis. Hydrolytic and fermentative bacteria causes
the breakdown of proteins, carbohydrates and fats into simpler acids, alcohols, neu-
tral compounds and some carbon monoxide (CO) and hydrogen (H2 ) by means of
hydrolysis and fermentation processes. Methane-forming bacteria find it difficult to
consume the products of fermentation that are too complex. Acid-forming bacte-
ria aid transitional digestion further degradation to acetate, hydrogen and carbon
dioxide. Traces of oxygen in the feedstock are consumed in this step, which bene-
fits oxygen-sensitive, methane-forming bacteria. The final step involves the use of
methane-forming bacteria to convert acetate to methane by methanogenesis. The
resulting biogas is a mixture of primary methane (CH4 ) and carbon dioxide (CO2 ).
Most of the experiments produce biogas accounts 55–75% methane by volume. So, it
can be used as an alternative for natural gas in many applications once it was treated
to remove sulphur content. Biogas finds applications in engine generator sets, small
gas turbines and some kinds of fuel cells.

4.3 Thermal Gasification

Thermal gasification is a process in which conversion of carbon fuel into flammable

compounds comprising of CO, H2 , CH4 , CO2 and Nitrogen (N2 ). This gas generates
heat energy which is used to run the turbines and fuel cells. This method is applicable
for the high moisture containing biomass such as wastewater, manure and kelp. Gasi-
fication at supercritical conditions (600–650 °C and 300 bar) initiate the conversion
of biomass into gas within 2 min. After a series of upgrading and purification steps
resulted in the production of methane gas (Bensaid et al. 2012)

4.4 Fermentation

Fermentation occupies a major position in the biofuel markets. The conversion of

biomass to fuel involves pretreatment, enzymatic hydrolysis, fermentation and dis-
tillation processes (Lynd 1996). The pretreatment enhances the surface area of the
biomass and make them susceptible to hydrolysis. Simultaneous saccharification and
fermentation were done to ferment the sugar released during the process. Once it is
done, the alternative fermentation pathways lead to the production of ethanol.
Conversion of Biomass to Methanol and Ethanol 67

4.5 Fischer–Tropsch Technology

Combination of biomass gasification and subsequent catalytic upgradation of syngas

results in the formation of biofuel by means of fermentation process. A number of
microorganisms are able to utilize CO, CO2 and H2 as substrates for growth and
production. These include autotrophs, which use C1 compounds as their sole source
of carbon and hydrogen and their energy source resulted in the production of long-
chain hydrocarbons which is converted to green diesel (Boerrigter et al. 2003).

4.6 Fast Pyrolysis

Treatment of biomass at a temperature of about 400–500 °C in the absence of oxygen

with the residence time of about 1 s (Goyal et al. 2008; Bridgwater 2012). The major
disadvantage of this process involves the use of pyrolytic oils which contains high
content of oxygen and water make them low quality compared to other commercial
fuels (Sharma et al. 2015) and also it faces difficulty in storage (Brown and Holmgren
2009).

4.7 Transesterification

The process involves the extraction of oil from the seeds by treating with sodium
hydroxide or potassium hydroxide as a catalyst. This resulted in the production of
esters of long-chain fatty acids (Pandey and Press 2009). This process has limitations
in the separation of large amount of waste water during the separation and cleaning
of the catalyst and final product (Kim et al. 2004) (Fig. 1).

Fig. 1 Flowchart for types of process involved in the production of Biofuel

68 G. K. Devi et al.

5 Scope of Ethanol Production from Biomass Materials

The biosphere possesses tremendous variety of biomass feedstock of varying types

and quality. Organic feedstocks are subjected to biochemical conversion processes
and get convertible into useful resources by means of landfilling procedures. Non-
degradable organic components do not undergo any conversions and it requires a
series of pretreatment procedures. The chemistry of biomass components includes
cellulose, hemicellulose, lignin, sugars, hydrocarbons, water and ash. Biomass-based
fuels possess some advantageous properties when compared to carbon based as it
possesses low ash content and high reactivity. In the past century, the consumption
of fossil fuel has been increased, which results in the depletion of known petroleum
reserves (Sheehan et al. 1998). There is a need for the efficient alternative fuel which
has been done by employing modern technologies using range of bioresources.
Ethanol is also known as “wood based fuel”. Generally, Ethanol has been produced
as synthetic gas and also from a wide variety of biomass feedstocks and it is evaluated
as fuel for combustion engines. Bioethanol has been produced through fermentation
of carbohydrates mainly using corn starch. But there is a limitation and demand
for corn because it occupies great deal for food as well as it requires vast land for
feedstock production. The potential sources for the low-cost ethanol include crop
residues, wood chips, Sea grass and sawdust (Sun and Cheng 2002). Ethanol can
also be manufactured from lignocellulosic materials which are a portion of municipal
solid waste but once it is pretreated and hydrolyzed, the released sugar compounds
are fermented and converted to Ethanol. Modern Biotechnology offers the great
potential for the production ethanol by using enzymatic conversions.
The cost of production depends upon the process equipment design and the con-
version reactions. Initially involves the conversion of cellulose to glucose undergoes
series of reactions resulted in the production of ethanol. This involves enzymatic reac-
tions as well as acid pathways as the production cost was low. Later, the genetically
engineered fungal strain such as Rut C30 has been used for cellulose production. This
is a cost-effective procedure but it minimizes the release of inhibitory compounds.

5.1 Microbial Biomass in Ethanol Formation

Microbial fuel production is initially carried out by sugar fermentation by yeast to

yield ethanol. Yeast species are used in the industry to generate the biofuel using
renewable bioresources mainly the agricultural products. This was processed easily
to ferment the sugar required for the fermentation process. S. cerevisiae is the most
commonly employed yeast in industrial ethanol production by standard glycolysis
pathway as it tolerates a wide range of pH (Lin et al. 2012). The same strain has
genetically engineered using recombinant DNA technology to up-regulate the stress
Conversion of Biomass to Methanol and Ethanol 69

tolerance genes in order to overcome the inhibitory conditions during the produc-
tion of ethanol and resulted in high yield using xylose as source. Zymomonasmo-
bilis, an anaerobic Gram-negative bacterium exclusively converts glucose to alcohol
through Entner–Duodoroff (ED) pathway (Chozhavendhan et al. 2017). This pro-
cess faces difficulty in additional processing of feedstock which is not economi-
cally feasible. Agrawal et al. genetically manipulated the Z. mobilis, which resulted
in the enhancement fermentative capability of the organism. E. coli is the exten-
sively studied model organism, which is metabolically engineered and it optimized
extensively for ethanol production. Recently, a thermophilic bacterium, Geobacillus-
Thermoglucosidasius has been genetically modified by expressing pyruvate decar-
boxylase from gluconobacteroxydans and reported for high ethanol yield as high as
1.37 mol ethanol/mol glucose.

6 Scope of Methanol Production from Biomass Materials

Methanol has been used as a promising alternative automotive fuel around the globe.
It is employed as clean fuel at a reasonable cost. The alkali-promoted metal catalyst
plays an important role in the synthesis of methanol from syngas. The choice of
the catalyst and the reaction time plays an important role in the production because
the copper-containing catalyst resulted in undesirable effect on the atmosphere. The
major limitation in the design of reactor for the methanol production involves the
removal of heat of reaction and thermodynamic imitations in order to enhance the
conversion efficiency (Spath and Dayton 2003).
Biomass-derived syngas can be used to generate methane, which can be employed
efficiently as transportation fuel. During the gasification, the carbon dioxide released
as a byproduct which can be used to store electricity (Hashimoto et al. 1999). Super-
critical water gasification technology is an exemplary method of biomethane gener-
ation with various kinds of biomass feedstocks.

6.1 Microbial Biomass in Methanol Formation

Methanotrophs has been used to produce biofuels by means of oxidation reactions

with the help of enzymes such as methane monoxygenase, methane dehydrogenase,
formaldehyde dehydrogenase. This was successfully achieved by using the geneti-
cally modified methanotrophic bacteria MethylosinusTrichosporium IMV 3011 was
to produce methanol through sequential reactions catalyzed by a series of enzymes.
The optimum production was about 20% along with other gases without loss of
productivity. Algae species such as Spirogyra and Chlorococcum species contains
large amount of polysaccharides, which acts as an excellent source of fuel production
with 65% efficiency. These polysaccharides can be extracted to fermentable sugars
70 G. K. Devi et al.

through hydrolysis and further fermentation to bioethanol and separated through

distillation process.

7 Applications

Primary alcohols include methanol, ethanol, butanol and propanol. Ethanol and
butanol can be produced from any substrate if it contains carbon molecules and
is considered as renewable and biodegradable and becomes a choice of fuel for con-
sumption (Khaled et al. 2016). Ethanol and methanol can be biologically produced
directly from fermentable feedstock’s, starchy materials and lignocellulosic mate-
rials and from industrial and urban wastes in large quantity without disturbing the
food chain (Praveen Kumar et al. 2014; Chozhavendhan et al. 2016). The major
application of alcohols from microbial biomass includes increased national security
and self-sufficiency because of lessened dependence on other countries. A better
balance of trade with enhanced technical sophistication and increased employment,
particularly in rural areas with a less toxic gas emission and a rapid expansion of
chemical industries.
Other common applications are as fuel; both alcohols are higher exhaust gas
recirculation and compression ratio with higher octane value compared with fossil
fuels. This can be used as a replacement for petroleum fuels in heat and power
generation field (Nigam and Singh 2011). Both the alcohols are used as anti-freezing
agent and also used in many industrial products such as paints and tincture. Ethanol
and methanol are polar solvent with dielectric constant and therefore can be used for
frequency dependent (Pace et al. 1968).

8 Conclusion

Microbial biomass is expected to be the major feedstock for ethanol production in

near future. The process of conversion is easy when compared to the conversion
of lignocellulosic feedstocks. In this platform, substrate cost is reduced by using
the microbial enzymes available that efficiently do the conversion process. This
led the researchers working to engineer microorganism for industrial production
of ethanol using genetic engineering techniques. Significant improvements can be
made to enhance the production of biofuels using microbial biomass by creating the
tolerance to inhibitors.
Conversion of Biomass to Methanol and Ethanol 71

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