Energy Sources, Part A

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Biomethanol Production from Organic Waste

Materials

A. Demirbas

To cite this article: A. Demirbas (2008) Biomethanol Production from Organic Waste Materials,
Energy Sources, Part A, 30:6, 565-572, DOI: 10.1080/15567030600817167

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Energy Sources, Part A, 30:565–572, 2008
Copyright © Taylor & Francis Group, LLC
ISSN: 1556-7036 print/1556-7230 online
DOI: 10.1080/15567030600817167

Biomethanol Production from

Organic Waste Materials

A. DEMIRBAS1
1
Sila Science, Trabzon, Turkey

Abstract Methanol is mainly manufactured from natural gas, but biomass can also
be gasified to methanol. Methanol can be produced from hydrogen-carbon oxide
mixtures by means of the catalytic reaction of carbon monoxide and some carbon
dioxide with hydrogen. Biosynthesis gas (bio-syngas) is a gas rich in CO and H2
obtained by gasification of biomass. Biomass sources are preferable for biomethanol
than for bioethanol because bioethanol is a high-cost and low-yield product. This is a
promising alternative, with a diversity of fuel applications with proven environmental,
economic, and consumer benefits. A mixture of gases from organic waste materials
is converted to methanol in a conventional steam-reforming/water-gas shift reaction
followed by high-pressure catalytic methanol synthesis.

Keywords biomass, biomethanol, biosynthesis gas, gasification, pyrolysis

Introduction
The transport sector is a major consumer of petroleum fuels such as diesel, gasoline,
liquefied petroleum gas (LPG), and compressed natural gas (CNG). This sector is likely to
suffer badly because of the following reasons: (a) Prices of petroleum in the global market
are on a rising trend; (b) Petroleum reserves are limited, and it is a monopoly of some oil-
importing countries, and the rest of the world depends on them; (c) Number of vehicles
based on petroleum fuels is on the increase worldwide. For these reasons, many research
programs recently focused on the development of concepts such as renewable resources,
sustainable development, green energy, eco-friendly process, etc., in the transportation
sector. Table 1 shows the potential and available motor fuels.
Worldwide energy consumption has increased 17-fold in the last century, and emis-
sions of CO2 , SO2 , and NOx from fossil-fuel combustion are primary causes of at-
mospheric pollution (Türe et al., 1997). Known petroleum reserves are estimated to be
depleted in less than 50 years at the present rate of consumption (Sheehan et al., 1998). In
developed countries there is a growing trend toward employing modern technologies and
efficient bioenergy conversion using a range of biofuels, which are becoming cost-wise
competitive with fossil fuels (Puhan et al., 2005).
Methanol is also known as “wood alcohol.” Generally, methanol is easier to find
than ethanol. Sustainable methods of methanol production are currently not economically
viable. Methanol is produced from synthetic gas or biogas and evaluated as a fuel for
internal combustion engines. The production of methanol is a cost-intensive chemical

Address correspondence to Prof. Ayhan Demirbas, P.K. 216, 61065 Trabzon, Turkey. E-mail:
ayhandemirbas@hotmail.com

565
566 A. Demirbas

Table 1
Potential and available motor fuels

Fuel type Available motor fuel

Traditional fuels Diesel and gasoline

Oxygenated fuels Ethanol 10% (E10), methanol, methyl tertiary butyl ether
(MTBE), ethyl tertiary butyl ether (ETBE), tertiary butyl
alcohol (TBA), and tertiary amyl methyl ether (TAME)
Alternative fuels Liquefied petroleum gases (LPG), ethanol 85% (E85), ethanol
95% (E95), methanol 85% (M85), methanol neat (M100),
compressed natural gas (CNG), liquefied natural gas (LNG),
bio-diesel (BD), hydrogen, and electricity

process. Therefore, in current conditions, only waste biomass such as old wood or bio-
waste is used to produce methanol (Vasudevan et al., 2005).
Methanol is poisonous and burns with an invisible flame. Methanol has, like ethyl
alcohol, a high octane rating, and hence an Otto engine is preferable. If an ignition booster
is used, methanol can be used in a diesel engine. One liter of gasoline corresponds to 2.2
liters of methanol, which means that larger tanks are needed for the same range. Most
processes require supplemental oxygen for the intermediate conversion of the biomass
into a synthetic gas (H2 C CO). A readily available supply of hydrogen and oxygen,
therefore, should improve the overall productivity of biomass-derived methanol (Ouellette
et al., 1997).
Currently, biomass converts to bio-oil by fast pyrolysis, and then the bio-oil converts
to hydrogen by catalytic steam reforming (Wang et al., 1997; Wang et al., 1998; Czernik
et al., 2000). The yield of hydrogen that can be produced from biomass is relatively low,
16–18% based on dry biomass weight (Demirbas, 2001). Only the carbohydrate-derived
bio-oil fraction produced from biomass undergoes reforming. At present, the amount of
biomass-derived bio-oil available for reforming is rather limited, but a viable way to
increase the production of hydrogen in a biomass-based plant could be co-reforming of
bio-oil with natural gas (Demirbas, 2005a). If the purpose were to maximize the yield of
liquid products resulting from biomass pyrolysis, a low temperature, high heating rate,
short gas residence time process would be required. If the purpose were to maximize the
yield of fuel gas resulting from biomass pyrolysis, a high temperature, low heating rate,
long gas residence time process would be preferred (Demirbas, 2004a).

Methanol Production Processes

Before modern production technologies were developed in the 1920s, methanol was
obtained from wood as a co-product of charcoal production and, for this reason, was
commonly known as wood alcohol. Methanol is currently manufactured worldwide by
conversion or derived from syngas, natural gas, refinery off-gas, coal, or petroleum:

2H2 C CO ! CH3 OH (1)

The chemical composition of syngas from coal and then from natural gas can be identical
with the same H2 /CO ratio. A variety of catalysts are capable of causing the conversion,
 Biomethanol Production from Organic Waste Materials 567

Table 2
Main production facilities of methanol and biomethanol

Methanol Biomethanol

Catalytic synthesis from CO and H2 Catalytic synthesis from CO and H2

Natural gas Distillation of liquid from wood pyrolysis
Petroleum gas Gaseous products from biomass gasification
Distillation of liquid from coal pyrolysis Synthetic gas from biomass and coal

including reduced NiO-based preparations, reduced Cu/ZnO shift preparations, Cu/SiO2

and Pd/SiO2 , and Pd/ZnO (Iwasa et al., 1993; Takezawa et al., 1987).
Methanol is currently made from natural gas but can also be made using biomass
via partial oxidation reactions (Demirbas and Gullu, 1998). Biomass and coal can be
considered as a potential fuel for gasification and further syngas production and methanol
synthesis (Takazewo et al., 1987). Sufficient hydrogen added to the synthesis gas to
convert all of the biomass carbon into methanol carbon would more than double the
methanol produced from the same biomass base (Phillips et al., 1990). Waste material can
be partially converted to methanol, for which the product yield for the conversion process
is estimated to be 185 kg of methanol per metric ton of solid waste (Brown et al., 1952;
Sorensen, 1983). Agriculture-(m)ethanol is at present more expensive than synthesis-
ethanol from ethylene and than methanol from natural gas (Grassi, 1999). Table 2 shows
main production facilities of methanol and biomethanol.
Biomass resources can be used to produce methanol. The pyroligneous acid obtained
from wood pyrolysis consists of about 50% methanol, acetone, phenols, and water
(Demirbas and Gullu, 1998; Gullu and Demirbas, 2001). As a renewable resource,
biomass represents a potentially inexhaustible supply of feedstock for methanol produc-
tion. The composition of syngas from biomass for producing methanol is presented in
Table 3. Current natural gas feedstocks are so inexpensive that, even with tax incentives,
renewable methanol has not been able to compete economically. Technologies are being
developed that may eventually result in commercial viability of renewable methanol.
Methanol from coal could be a very important source of liquid fuel in the future.
The coal is first pulverized and cleaned, then fed to a gasifier bed where it is reacted
with oxygen and steam to produce the syngas. Once these steps have been taken, the
production process is much the same as with the other feedstocks, with some variations
in the catalyst used and the design of the converter vessel in which the reaction is
carried out. Methanol made using synthesis gas (syngas) with hydrogen and carbon
monoxide is in a 2 to 1 ratio (Table 3). The syngas was transformed to methanol in
a fixed catalyst bed reactor. Coal-derived methanol has many preferable properties; it

Table 3
Composition of syngas from biomass for producing methanol (vol%)

H2 CO CH4 CO2 C 2 H4 H2 O N2

32–41 21–29 10–15 14–19 0.8–1.2 5.5–6.5 0.6–1.2

Source: Gullu and Demirbas, 2001.
568 A. Demirbas

is free of sulfur and other impurities and could replace petroleum in transportation or
be used as a peaking fuel in combustion turbines, or supply a source of hydrogen for
fuel cells. The technology for making methanol from natural gas is already in place and
requires only efficiency improvements and scale-up to make methanol an economically
viable alternative transportation fuel (Demirbas, 2005b).
In recent years, a growing interest has been observed in the application of methanol
as an alternative liquid fuel, which can be used directly for powering Otto engines or
fuel cells (Chmielniak and Sciazko, 2003). The feasibility of achieving the conversion
has been demonstrated in a large scale system in which a product gas is initially produced
by pyrolysis and gasification of a carbonaceous matter. Syngas from biomass is altered
by catalyst under high pressure and temperature to form methanol. This method will
produce 100 gallons of methanol per ton of feed material (Rowell and Hokanson, 1979).
The gases produced can be steam reformed to produce hydrogen and followed by
water-gas shift reaction to further enhance hydrogen production. When the moisture
content of biomass is higher than 35%, it can be gasified in a supercritical water condition
(Hao and Guo, 2002). Supercritical water gasification is a promising process to gasify
biomass with high moisture contents due to high gasification ratio (100% achievable)
and high hydrogen volumetric ratio (50% achievable) (Yoshida et al., 2004; Matsumura
and Minowa, 2004; Demirbas, 2004b). Hydrogen produced by biomass gasification was
reported to be comparable to that by natural gas reforming (Bowen et al., 2003). The
process is more advantageous than fossil fuel reforming in consideration of environmental
benefits. It is expected that biomass thermochemical conversion will be one of the most
economical large-scale renewable hydrogen technologies.
The strategy is based on producing hydrogen from biomass pyrolysis using a co-
product strategy to reduce the cost of hydrogen and concludes that only this strategy
could compete with the cost of the commercial hydrocarbon-based technologies (Wang
et al., 1998). This strategy will demonstrate how hydrogen and bio-fuel are economically
feasible and can foster the development of rural areas when practiced on a larger scale.
The process of biomass to activated carbon is an alternative route to hydrogen with a
valuable co-product that is practiced commercially (Demirbas, 2006).
The simultaneous production of bio-methanol (obtained by the hydrogenation of
CO2 developed during the fermentation of sugar juice), in parallel to the production
of bio-ethanol, appears economically attractive in locations where hydro-electricity is
available at very low cost (0.01$ Kwh) and where lignocellulosic residues are available
as surpluses (Grassi, 1999).
The gas is converted to methanol in a conventional steam-reforming/water-gas shift
reaction followed by high-pressure catalytic methanol synthesis:

CH4 C H2 O ! CO C 3H2 (2)

CO C H2 O ! CO2 C H2 (3)

Equations (2) and (3) are called gasification/shift reactions.

CO C 2H2 ! CH3 OH (4)

or
CO2 C 3H2 ! CH3 OH C H2 O (5)
 Biomethanol Production from Organic Waste Materials 569

Figure 1. Biomethanol from carbohydrates by gasification and partial oxidation with O2 and H2 O.

Equations (4) and (5) are methanol synthesis reactions. Figure 1 shows production of
biomethanol from carbohydrates by gasification and partial oxidation with O2 and H2 O.
The energy value of residues generated worldwide in agriculture and the forest-
products industry amounts to more than one-third of the total commercial primary energy
use at present (Hall et al., 1993). Bio-energy supplies can be divided into two broad
categories: (1) organic municipal waste and residues from the food and materials sectors,
and (2) dedicated energy crops plantations. Bio-energy from biomass, both residues and
energy crops, can be converted into modern energy carriers such as hydrogen, methanol,
ethanol, or electricity (Azar et al., 2003).
Methanol can be produced from biomass essentially by any primary energy source.
Thus, the choice of fuel in the transportation sector is to some extent determined by
the availability of biomass. As regards the difference between hydrogen and methanol
production costs, conversion of natural gas, biomass, and coal into hydrogen is generally
more energy efficient and less expensive than conversion into methanol (Azar et al.,
2003).

Methanol Use
Methanol is commonly used in biodiesel production for its reactivity. Methanol can be
used as one possible replacement for conventional motor fuels. The use of methanol as a
motor fuel received attention during the oil crises of the 1970s due to its availability and
low cost. Problems occurred early in the development of gasoline-methanol blends. As a
570 A. Demirbas

result of its low price, some gasoline marketers over blended. Many tests have shown
promising results using methanol 85–100 vol% as a transportation fuel in automobiles,
trucks, and buses. Methanol can be used in blend with conventional fuels without engine
modification or pure as a fuel. It can be used in traditional combustion engines and
indirect methanol fuel cells. Methanol is also being viewed as an excellent base fuel
for fuel cell vehicles. It can also be used as a base product for making biodiesel from
vegetable oils (Demirbas, 2006).
Methanol can be used as one possible replacement for conventional motor fuels. It
has been seen as a possible large volume motor fuel substitute at various times during
gasoline shortages. It was often used in the early part of the century to power automobiles
before inexpensive gasoline was widely introduced. In the early 1920s, some viewed it
as a source of fuel before new techniques were developed to discover and extract oil.
Synthetically produced methanol was widely used as a motor fuel in Germany during
World War II.
Biomass appears to be an attractive feedstock for three main reasons. First, it
is a renewable resource that could be sustainably developed in the future. Second, it
appears to have formidably positive environmental properties resulting in no net releases
of carbon dioxide and very low sulfur content. Third, it appears to have significant
economic potential, provided that fossil fuel prices increase in the future (Cadenas and
Cabezudo, 1998). Lignocellulosic bio-methanol have such low emissions because the
carbon content of the alcohol is primarily derived from carbon that was sequestered
in the growing of the bio-feedstock and is only being re-released into the atmosphere
(Difiglio, 1997).

Conclusion
The term biofuel is used mainly to refer to liquid fuels. Biomethaanol or biomass derived
methanol is a biofuel. Methanol is currently made from natural gas but can be made
using wood waste or garbage via partial oxidation reaction into syngas, followed by
catalytic conversion into methanol called biomethanol. Methanol is commonly used in
biodiesel production for its reactivity. Methanol can be used as one possible replacement
for conventional motor fuels. There are several reasons for biofuels to be considered
as relevant technologies by both developing and industrialized countries. These include
energy security reasons, environmental concerns, foreign exchange savings, and socio-
economic issues related to the rural sector.
Methanol is currently made from natural gas but can also be made using biomass
via partial oxidation reactions. Biomass and coal can be considered as potential fuels
for gasification and further syngas production and methanol synthesis. Biomass sources
are preferable for biomethanol than for bioethanol because bioethanol is a high-cost,
low-yield product.
Methanol can be used as one possible replacement for conventional motor fuels
without engine modification or pure as a fuel. It can be used in traditional combustion
engines and indirect methanol fuel cells. It can also be used as a base product for making
biodiesel from vegetable oils. In comparison with gasoline, methanol is a superior engine
fuel. Thermal efficiency values for the engine are higher, and there are no emission
problems.
An important reason for interest in renewable energy sources is the concern for
the greenhouse effect. Development of alternative motor fuels, especially obtained from
 Biomethanol Production from Organic Waste Materials 571

renewable energy sources such as biomethanol, biodiesel, and hydrogen can work to
fulfill this commitment. Methanol benefits the environment, economy, and consumers.

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