Professional Documents
Culture Documents
Center for Rural Development and Technology, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110016, India
Catalysis and Chemical Reaction Engineering Laboratories, Department of Chemical Engineering, University of Saskatchewan, Saskatoon, Saskatchewan S7N 5A9, Canada
c
Department of Chemical Engineering, Indian Institute of Technology Guwahati, North Guwahati, Assam, India
b
A R T I C L E I N F O
A B S T R A C T
Article history:
Received 3 August 2009
Accepted 9 October 2009
Sustainable economic and industrial growth requires safe, sustainable resources of energy. For the future
re-arrangement of a sustainable economy to biological raw materials, completely new approaches in
research and development, production, and economy are necessary. The rst-generation biofuels
appear unsustainable because of the potential stress that their production places on food commodities.
For organic chemicals and materials these needs to follow a biorenery model under environmentally
sustainable conditions. Where these operate at present, their product range is largely limited to simple
materials (i.e. cellulose, ethanol, and biofuels). Second generation bioreneries need to build on the need
for sustainable chemical products through modern and proven green chemical technologies such as
bioprocessing including pyrolysis, Fisher Tropsch, and other catalytic processes in order to make more
complex molecules and materials on which a future sustainable society will be based. This review focus
on cost effective technologies and the processes to convert biomass into useful liquid biofuels and
bioproducts, with particular focus on some biorenery concepts based on different feedstocks aiming at
the integral utilization of these feedstocks for the production of value added chemicals.
2009 Elsevier Ltd. All rights reserved.
Keywords:
First generation biofuel
Second generation biofuel
Biorenery
Biomass
Bio-oil
Contents
1.
2.
3.
4.
5.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Biomass as multiple feedstocks for biorenery . . . . . . . . . . .
2.1.
Biorenery concept/system . . . . . . . . . . . . . . . . . . . . .
First generation biofuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.
Conversion processes for rst generation biofuels . . .
3.1.1.
Transesterication . . . . . . . . . . . . . . . . . . . . .
3.2.
Whole-crop biorenery . . . . . . . . . . . . . . . . . . . . . . . .
3.2.1.
Oleochemicals . . . . . . . . . . . . . . . . . . . . . . . .
3.2.2.
De-oil cake . . . . . . . . . . . . . . . . . . . . . . . . . . .
Second generation biofuels . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.
Conversion processes for second generation biofuels .
4.1.1.
Physical conversion . . . . . . . . . . . . . . . . . . . .
4.1.2.
Thermo-chemical conversion . . . . . . . . . . . .
4.1.3.
Hydrotreating of vegetable oils/green diesel
4.1.4.
Bio-oil. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.5.
FT oil or green motor fuel from biomass . . .
4.1.6.
Bioethanol from lignocellulosic biomass . . .
4.1.7.
Chemical conversion . . . . . . . . . . . . . . . . . . .
Types of biorenery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.1.
Green biorenery . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.2.
Forest and lignocellulosic based biorenery . . . . . . . .
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* Corresponding author at: Center for Rural Development and Technology, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110016, India.
Tel.: +91 11 26591162; fax: +91 11 26591121.
E-mail addresses: snn@rdat.iitd.ac.in, naiksn@gmail.com (S.N. Naik).
1364-0321/$ see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.rser.2009.10.003
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S.N. Naik et al. / Renewable and Sustainable Energy Reviews 14 (2010) 578597
6.
5.3.
Aquatic or algae-based biorenery
5.4.
Integrated biorenery . . . . . . . . . . .
Conclusions . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgements . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . .
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1. Introduction
In the twentieth century major research emphasis was given for
the development of petroleum, coal, and natural gas based renery
to exploit the cheaply available fossil feed stock. These feedstocks
are used in industry to produce multiple products such as fuel, ne
chemicals, pharmaceuticals, detergents, synthetic ber, plastics,
pesticides, fertilizers, lubricants, solvent, waxes, coke, asphalt, etc.
to meet the growing demand of the population [1,2]. Currently, the
fossil resources are not regarded as sustainable and questionable
from the economic, ecology and environmental point of views [3].
The burning of fossil fuels is a big contributor to increasing the
level of CO2 in the atmosphere which is directly associated with
global warming observed in recent decades [4]. The adverse effects
of greenhouse gas (GHG) emissions on the environment, together
with declining petroleum reserves, have been realized. Therefore,
the quest for sustainable and environmentally benign sources of
energy for our industrial economies and consumer societies has
become urgent in recent years [5]. Consequently, there is renewed
interest in the production and use of fuels from plants or organic
waste.
The biofuels produced from the renewable resources could help
to minimize the fossil fuel burning and CO2 production. Biofuels
produced from biomass such as plants or organic waste could help
to reduce both the worlds dependence on oil and CO2 production.
These biofuels have the potential to cut CO2 emission because the
plants they are made from use CO2 as they grow [6]. Biofuels and
bioproducts produced from plant biomass would mitigate global
warming. This may due to the CO2 released in burning equals the
CO2 tied up by the plant during photosynthesis and thus does not
increase the net CO2 in the atmosphere. Additionally, biofuel
production along with bioproducts can provide new income and
employment opportunities in rural areas. 21st Century is looking
for a shift to alternate industrial feedstock and green processes to
produce these chemicals from renewable biomass resources [7].
First generation biofuels can offer some CO2 benets and can
help to improve domestic energy security. But concerns exist about
the sourcing of feedstocks, including the impact it may have on
biodiversity and land use and competition with food crops. A rst
generation biofuel (i.e. biodiesel (bio-esters), bio-ethanol, and
biogas) is characterized either by its ability to be blended with
petroleum-based fuels, combusted in existing internal combustion
engines, and distributed through existing infrastructure, or by the
use in existing alternative vehicle technology like FFVs (Flexible
Fuel Vehicle) or natural gas vehicles. The production of 1st
generation biofuels is commercial today, with almost 50 billion
liters produced annually. There are also other niche biofuels, such
as biogas which have been derived by anaerobic treatment of
manure and other biomass materials. However, the volumes of
biogas used for transportation are relatively small today [4].
However, the rst generation biofuels seems to create some
skepticism to scientists. There are concerns about environmental
impacts and carbon balances, which sets limits in the increasing
production of biofuels of rst generation. The main disadvantage of
rst generation biofuels is the food-versus-fuel debate, one of the
reasons for rising food prices is due to the increase in the
production of these fuels [8]. Additionally it is claimed that
biodiesel is not a cost efcient emission abatement technology.
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S.N. Naik et al. / Renewable and Sustainable Energy Reviews 14 (2010) 578597
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S.N. Naik et al. / Renewable and Sustainable Energy Reviews 14 (2010) 578597
583
potential to replace homogeneous catalysts, eliminating separation, corrosion and environmental problems [23].
The solid acid catalyzed biodiesel production by simultaneous
esterication and transesterication of low quality oil containing
high FFA was performed by Kulkarni et al. [23]. The reaction
(1)
584
S.N. Naik et al. / Renewable and Sustainable Energy Reviews 14 (2010) 578597
Fig. 5. (a) Dry mill process and (b) Wet mill process.
S.N. Naik et al. / Renewable and Sustainable Energy Reviews 14 (2010) 578597
yeast
! 2C2 H5 OH 2CO2
246
244
585
has several advantages. First low sulphur, low ash fuels can be
made for commercial use. Second, liquid fuel is much easier to
handle, store and transport than gaseous products. By utilizing
waste lignocellulosic biomass through anaerobic digestion process
will generate liquid fuel and biofertilizer for Agricultural production. The biorenery concept of anaerobic digestion is shown in
Fig. 6.
3.2. Whole-crop biorenery
A whole-crop biorenery processes and consumes the whole
crop to obtain useful products. Raw materials such as oil seed can
be used as feedstock in the unit operations of a whole crop
biorenery as depicted in Fig. 4. In that context, example of
jatropha oil seed crop has been discussed. Jatropha seed kernel
contains 3540% oil and 11.5 tonnes of oil can be produced per ha
[28]. The process of converting biomass into energy is initiated by
separation of biomass into different components that are then
treated separately. The oil obtained acts as the starting material for
biodiesel production or can undergo chemical modication to
produce oleochemical products, whereas the de-oil cake fraction
after purication can be used as the basic raw materials for the
synthesis of valuable chemicals or for gasication. The lignocellulosic biomass produced during the renery operations can act as
the starting material to the lignocellulosic biorenery for the
production of syngas, where syngas can be used as the basic
material for the synthesis of fuels and methanol using the Fischer
Tropsh process.
3.2.1. Oleochemicals
Oleochemicals refer to chemicals derived from natural oils and
fats of both plant and animal origins. Basically, oleochemicals refer
to the fatty acids and glycerol derived from the splitting of the
triglyceride structures of oils and fats. However, they also include
those derivatives derived from the subsequent modication of the
carboxylic acid group of the fatty acids by chemical or biological
means, and other compounds obtained from further reactions of
these derivatives. Oleochemicals are often categorised into basic
oleochemicals such as fatty acids, fatty methyl esters, fatty
alcohols, fatty amines and glycerol which are highlighted as bold
in schematic, and their further downstream derivatives obtained
from further chemical modications of these basic oleochemicals
are highlighted in italics and shown in Fig. 7a and b.
In fact, until the1980s, almost 95% of natural oils and oils were
used in foods and only a small percentage was used in non-food
applications such as soap manufacturing and drying oils. It was
only after the 1980s that oleochemicals found wide uses in both
food and non-food, or technical applications which previously are
the domains of synthetic chemicals derived from petroleum or
better known as petrochemicals. At this moment, oleochemicals
are used in the manufacture of such products as foods and specialty
fats, soaps and detergents, cosmetics and personal care products,
lubricants and greases, drying oil, surface coatings and polymers,
586
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Fig. 7. (a) Basic oleochemicals and downstream oleochemicals and derivatives and (b) basic oleochemicals and downstream oleochemicals and derivatives production
ow.Soon [29].
S.N. Naik et al. / Renewable and Sustainable Energy Reviews 14 (2010) 578597
587
Table 1
Application of oleochemicals.
Industry/Product
Uses
Leather
Metal Work and Foundry
Mining
Rubber
Electronics
Lubricants and Hydraulic Fluids
Paints and Coatings
Printing and Paper Re-cycling
Plastics
Biofuels
Waxes
Soaps & Detergents
Health & Personal Care
Food
Animal Feeds
Soon [29].
588
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589
590
S.N. Naik et al. / Renewable and Sustainable Energy Reviews 14 (2010) 578597
Table 2
Green diesel fuel properties.
% oxygen
Specic gravity
Sulphur (ppm)
Heating value (MJ/kg)
Cloud point (8C)
Distillation (8C)
Cetane
Stability
Petroleum
ULSD
Biodiesel
(FAME)
Green
diesel
0
0.84
<10
43
5
200350
40
Good
11
0.88
<1
38
5 to +15
340355
5065
Marginal
0
0.78
<1
44
10 to 20
265320
7090
Good
diesel, and biodiesel. Green diesel has a higher cetane value and
good cold ow properties. It is also has excellent storage stability
and is completely compatible for blending with the standard mix
of petroleum derived diesel fuels. In contrast to fatty acid methyl
esters, green diesel properties do not depend on feed origin and
process conguration and the fully deoxygenated biofuel is readily
blended with diesel fuel.
4.1.4. Bio-oil
Bio-oil/pyrolysis oil is produced by fast pyrolysis process. In this
process, organic class of compounds, such as cellulose, hemicellulose, and lignin, etc. are thermally decomposed at moderate
temperature (400600 8C) in absence of oxygen to produce liquid
product viz. bio-oil (6070%), char (1325%), and gas such as CO,
H2, light hydrocarbons (1325%). The yield and chemical
composition of bio-oil depends upon feed stocks and process
condition: particle size of biomass (25 mm), residence time (0.1
2 s), and reactor type. In general, reactor types which are presently
used are; uidized bed reactor, circulating uid bed, fast uidized
bed, etc. (Fig. 11). The bio-oil is a dark brown viscous, corrosive and
acidic with distinctive smoky odor used as fuel for boiler, gas
turbine, diesel engines, furnaces and stationary engines. Bio-oil has
a complex chemical composition contained chemical products of
lignocelluloses biomass like aliphatic alcohols/aldehydes, furanoids, pyranoids, benzenoids, fatty acids and high molecular mass
hydrocarbons, etc. these constituents are mixed with water (25
45%), which is formed in pyrolysis process to form an emulsion
with organic constituents. Therefore a wide range of Green
S.N. Naik et al. / Renewable and Sustainable Energy Reviews 14 (2010) 578597
591
Table 3
Ethanol from renewable lignocellulosic feedstocks.
S. no
Feedstocks
1
2
3
4
5
Cane bagasses
Corn stover
Rice straw
Forest residue
Saw dust
424
428
416
310
382
DH 165 kJ=mol
S.N. Naik et al. / Renewable and Sustainable Energy Reviews 14 (2010) 578597
592
Table 4
Fuel properties of ethanol, gasoline, blended gasoline.
Property
Ethanol
Gasoline
E10
E20
Specic gravity
Heating value
Vapor pressure
Oxygen content
0.79
76000
17
35
0.720.75
117000
59.5
0
0.730.76
112900
64
3.5
0.740.77
109000
63.4
7
Shelley [25].
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593
5. Types of biorenery
5.1. Green biorenery
A green biorenery is a multiproduct system which handles its
renery cuts, products, and fractions in accordance with the
physiology of the corresponding plant material as described by
Kamm and Kamm [21], Fernando et al. [12] and illustrated in
Fig. 15. A green biorenery uses natural wet feedstocks derived
from untreated products, such as grass, green plants, or green crops
as inputs, which are produced in large quantities in green plants.
The rst step of the renery is to treat the green biomass
substances in their natural form using wet-fractionation to
produce a ber-rich press cake and a nutrient-rich green juice.
The press cake contains cellulose, starch, valuable dyes and
pigments, crude drugs, and other organics, whereas the green juice
includes proteins, free amino acids, organic acids, dyes, enzymes,
hormones, other organic substances, and minerals. The pressed
cake can be also used for the production of green feed pellets, as a
raw material for the production of chemicals, such as levulinic acid,
and for conversions to syngas and synthetic fuels.
5.2. Forest and lignocellulosic based biorenery
Lignocellulosic materials contain two types of polysaccharides,
cellulose and hemicellulose, bound together by a third component,
lignin. LCB consists of three basic chemical fractions, (i)
hemicellulose, sugar molecule of mainly pentoses, (ii) cellulose,
a glucose polymer, (iii) lignin, polymer of phenols [54]. An
overview of potential products of LCB is shown in Fig. 16. In LCB
594
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syngas stage, biogas stage, carbon rich chains, and plant products.
The concept of LCB based on these stages is described in Fig. 16.
5.3. Aquatic or algae-based biorenery
S.N. Naik et al. / Renewable and Sustainable Energy Reviews 14 (2010) 578597
595
example, palm oil, one of the most productive oil crops yields only
6000 l of oil per hectare, whereas microalgae oil yield per hectare is
around 58,700 l/ha [57]. The potential advantages of algae as
feedstocks (biofuels and biomaterials) for biorenery are as
follows (Fig. 18).
(1) Algae synthesize and accumulate large quantities of neutral
lipids/oil (2050% DCW), (2) High growth rates (13 doublings/
day), (3) Thrives in saline/brackish water/costal sea water, (4)
Algae tolerate marginal lands (e.g. desert, arid and semi arid land)
that are not suitable for conventional agriculture, (5) Utilize
growth nutrients such as nitrogen and phosphorus from variety of
wastewater sources (e.g. Agricultural run off, industrial and
municipal waste water), (6) Sequester CO2 from ue gases emitted
from fossil fuel red power plants and other sources there by
reducing emissions of a major greenhouse gas, (7) Produced value
added co-products or by products (e.g. biopolymers, proteins,
Table 5
Physico-chemical properties of bo-oil produced from different biomass.
Properties
Wood
Cereals (wheat)
Density
Water content % (w/w)
pH
1111250
1530
2.83.8
1233
23.3
2.8
55.363.5
5.27.2
0.070.39
0.00.05
0.030.3
44115
22.530.2
56
58.4
6.0
0.1
0.08
50
16.6
>106
6972
9.810.8
3.35.4
13.114.6
36
35.5537.85
83
54.60
6.45
0.73
<0.10
0.05
4.1116.5
22.4
<90
596
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6. Conclusions
The paper has discussed rst and second generation biofuel,
concept of bioreneries, different types of bioreneries, and
S.N. Naik et al. / Renewable and Sustainable Energy Reviews 14 (2010) 578597
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