Rice Straw As A Feedstock For Biofuels Availability, Recalcitrance, and Chemical Properties

Review
Rice straw as a feedstock for

biofuels: Availability, recalcitrance,
and chemical properties
Alok Satlewal,* Department of Chemical and Biomolecular Engineering, University of Tennessee,
Knoxville, TN, USA; Joint Institute for Biological Sciences, Biosciences Division, Oak Ridge National
Laboratory (ORNL), TN, USA; Department of Bioenergy, DBT-IOC Centre for Advanced Bioenergy
Research, Research and Development Centre, Indian Oil Corporation Ltd, Faridabad, India
Ruchi Agrawal,* Department of Bioenergy, DBT-IOC Centre for Advanced Bioenergy Research,
Research and Development Centre, Indian Oil Corporation Ltd, Faridabad, India
Samarthya Bhagia and Parthapratim Das, Department of Chemical and Biomolecular Engineering,
University of Tennessee, Knoxville, TN, USA
Arthur J. Ragauskas, Department of Chemical and Biomolecular Engineering, University of
Tennessee, Knoxville, TN, USA; Department of Forestry, Wildlife and Fisheries, Center for Renewable
Carbon, University of Tennessee, Institute of Agriculture, Knoxville, TN, USA; Joint Institute for
Biological Sciences, Biosciences Division, Oak Ridge National Laboratory (ORNL), TN, USA
Received May 28, 2017; revised August 8, 2017; accepted August 10, 2017
View online at Wiley Online Library (wileyonlinelibrary.com)
DOI: 10.1002/bbb.1818; Biofuels, Bioprod. Bioref. (2017)
Abstract: The surplus availability of rice straw, its limited usage, and environmental pollution caused
by its inefficient burning has fostered research for its valorization to biofuels. This review elucidates
the current status of rice straw potential around the globe along with recent advances in revealing the
critical factors responsible for its recalcitrance and chemical properties. The role and accumulation
of high silica content in rice straw has been elucidated with its impact on enzymatic hydrolysis in a
biorefinery environment. The correlation of different pre-treatment approaches in modifying the physi-
ochemical properties of rice straw and improving the enzymatic accessibility has also been discussed.
This study highlights new challenges, resolutions, and opportunities for rice straw based biorefineries.
© 2017 Society of Chemical Industry and John Wiley & Sons, Ltd
Keywords: rice straw; biofuel; biochemicals; biopower; recalcitrance; pre-treatment
Introduction generating enormous biomass residues, and it is also a

silica-rich C3 crop grown in wetlands.1-3 According to the
ice straw is an attractive feedstock for energy pro- Food and Agriculture Organization (FAO) of the United
R duction because of its surplus availability around

the globe. It is a major food crop around the world
Nations, the world’s rice production touched a record of
760 million tons by 2017 July (1 ton or tonne is a metric
Correspondence to: Arthur J. Ragauskas, Department of Chemical and Biomolecular Engineering, University of Tennessee,
Knoxville, TN 37996, USA. E-mail: aragausk@utk.edu
*Alok Satlewal and Ruchi Agrawal contributed equally as first author
© 2017 Society of Chemical Industry and John Wiley & Sons, Ltd 1
A Satlewal et al. Review: Rice straw as a feedstock for biofuels
ton in the United States and it is equal to 1000 kilo- Rice ecosystems

grams or one megagram (Mg)).4 This generates approxi-
mately 1140 million tons of rice straw considering the fact The growing environment of rice is referred as ecosys-
that approximately 1.5 tons of rice straw is generated per tem which could be divided into distinct agro-ecological
ton of rice. About 50% of rice straw is burnt in the field zones referred to as upland, irrigated lowland, rainfed
while the remaining is utilized as fodder or used in the lowland, deepwater, and flooding ecosystems (Table 1).16,17
wood-composite industry, or left, as such, to decompose in Land utilized for upland rice production is found in Asia,
landfi lls.4-6 Inefficient burning of rice straw releases large Africa, and Latin America which is low-lying and drought-
amounts of harmful gases including carbon monox- prone and with steep slopes. Rice cultivation in this area
ide, polycyclic aromatic hydrocarbons, volatile organic is dependent on rainfall and therefore production yields
compounds, and nitrous oxides, along with suspended vary considerably from year to year. Irrigated lowland zone
particulate matter.6 This leads to alarming levels of envi- is dominant in flat low-lying flood areas of river deltas
ronmental pollution and represents a tremendous waste of like temperate and sub-tropical climate areas like South
lignocellulosic biomass resource. Hence, there is an Asia, Southeast Asia, and East Asia. Irrigated ecosystems
urgent need to develop high-volume, value-added conver- provide 75% of global rice production with maximum
sion technologies to harness the energy potential of sur- yields of about 3 to 10 tons/ha among these ecosystems.18
plus rice straw. Rainfed lowland rice ecosystems are found mainly in tropi-
In a recent study by Wu et al.,7 it was found that all rice cal climate areas like river deltas, flood plain, and inland
straw varieties under different chemical pre-treatments swamps and water supply comes principally from rain-
had high enzymatic digestibility in comparison with fall and from diverted small water courses (e.g. streams),
another major C3 food crop, i.e., wheat straw. This was or swollen rivers. Such areas as East India, Bangladesh,
partially attributed to its reduced lignin content and Indonesia, Philippines, and Thailand provide 25% of total
its distinct wall polymer features such as cellulose CrI, rice area used worldwide.18 Deepwater rice ecosystems are
hemicellulosic Xyl/Ara ratio, and lignin H/G propor- found in low lying areas in deltas, estuaries, swamps, and
tion.7 Instead of burning, if all rice straw were converted river valleys in tropical Asia and sub-Saharan Africa, where
into bioethanol, it would become the single largest feed- water remains stagnant for some time during rice-growing
stock for second-generation ethanol production in the season with standing water up to ~100 cm.19-21 Flooding/
world.8-10 In addition, rice straw may also be utilized as floating ecosystems are prevalent in South and Southeast
a feedstock for producing value-added chemicals and Asia, and are characterized by periods of extreme flooding
bio-derived materials via the biorefinery concept. This and drought with low and variable yields (Table 2).19-21
approach would help in reducing environmental pollution Oryza sativa (Asian rice) and Oryza glaberrima (African
and generating new employment opportunities in rural rice) are two major rice varieties grown all around the
districts. world.22,23 Other popular rice varieties grown in Asia,
The recalcitrant nature of rice straw is one of the chal- Africa, central and South America, Philippines, Australia,
lenges for the biochemical conversion of rice straw to and Indonesia are tabulated in Table 2. Area, plant height,
bioethanol production. It contains crystalline cellulose and rice yield of different regions of the world are tabu-
with a high degree of polymerization and branched low lated in Table 3. These results demonstrated that maxi-
molecular weight hemicellulose.2,11,12 These carbohydrates mum rice cultivation area is in India (418.5 lakh hectare)
are shielded, in part, by a lignin matrix which subse- followed by China (298.8 lakh hectare) and Indonesia
quently reduces their accessibility.13 Lignin is the second (128.8 lakh hectare) but maximum rice yield is located in
most available biopolymer on Earth but it is highly resist- the United States of America followed by China and Japan.
ant to biodegradation. However, unlike other crops, rice Rice plant height also varies from a minimum in China
has high silica accumulation in straw and it plays a signifi- (36.2 cm) to maximum in Thailand (600 cm).19,24-29
cant role in plant mechanical strength, cell wall polymer
features and wall-network remodeling but limited infor- Rice straw availability and usage
mation is available about its effect on saccharification and
fermentation.14,15 A comprehensive understanding of rice Rice is the third most important cereal crop in the world
straw structural constituents, physicochemical character- after maize (corn) and wheat. It is a primary staple food to
istics and pre-treatment approaches is necessary to har- provide energy and protein to more than half of the world
ness its full potential as a feedstock for biofuel. population. In July 2017, a record 686.4 million tons of rice
2 © 2017 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. (2017); DOI: 10.1002/bbb
Review: Rice straw as a feedstock for biofuels A Satlewal et al.
Table 1. Rice ecosystems around the world.19–21

Ecosystem Water source Regions Yield, (ton/Ha) Problems with cultivation Properties of the rice crop
Upland Rainfall Asia, Africa, 1.5 Drought prone, weed com- Good drought tolerance, matures
Latin America petition, production and earlier, develops deeper roots, and
yields are dependent on rain- has lower tillering rates; problems
fall, incidence of blast, and include weaker straw and greater
changes in soil nutrients susceptibility to lodging
Irrigated Irrigation South Asia, 3–10 — —
Lowland South east
asia, East Asia
Rainfed Rainfall East India, 1.5–2.5 Drought and floods, cultiva- —
Lowland Bangladesh, tion depends on seasonal
Indonesia, rainfall
Philippines,
Thailand
Deepwater Land covered with — <2 Poor stand establishment, Good seeding vigor, greater
50 cm to 100 cm high seedling mortality rates, submergence tolerance, and
water for more than weed competition, and enhanced ability to elongate
half of the crop’s drought damage at the ger-
growth period mination and seedling stages
resulting from direct-seeding
Flooding/ Land covered with — low and — —
Floating 1 m to 6 m for more variable
than half of the
crop’s growth period
was produced in Asia with India as the second-largest pro- mately 80% of nitrogen, 25% of phosphorus, 21% of potas-
ducer after China (Table 4).4 By exporting about 10.8 mil- sium and organic matter are removed) and kills most
lion tons of rice, India is expected to retain its top position of the beneficial insects and microorganisms in the soil
in 2017 followed by Thailand, Vietnam, Pakistan, and the which greatly affects soil productivity.34 Therefore, there
USA.30 Rice straw is a by-product generated after harvest- is an urgent need to develop new alternative methods for
ing of rice grains from the paddy. It is composed of panicle valorization of rice straw so that farmers receive higher
rachis, leaf blades, leaf sheaths, and stems.31 profits for rice straw collection from the fields and curb
The availability of rice straw across the continents is rice-straw burning that adds to pollution.
depicted in Fig. 1.30,32 Maximum theoretical ethanol pro-
duced from this was calculated on the basis of recently Rice-straw storage and bulk density
published chemical composition data. It showed about 350
million liters of ethanol could be produced in Asia which Rice straw has lower energy and density than fossil fuels
may replace a large chunk of gasoline.11,33 therefore, more biomass is needed to release same amount
Earlier, most of the rice straw grown was collected from of energy. For example, the bulk density of loose rice straw
paddy fields by conventional manual harvesting which is approximately 20–40 kg/m3 in comparison to coal at
allowed its utilization as a raw material for the pulp and 690–760 kg/m3.36 Since, it is difficult to store and transport
paper industry, fertilizer, and animal fodder. But the new biomass it has been suggested that storage and transport
combine-based harvesting methodology has made its col- of unprocessed biomass should be within a 200-km radius
lection quite expensive and tedious. Therefore, only 20% to make it economically feasible.37 Another approach to
of rice straw is utilized while approximately 50% is burnt address this issue is to improve biomass density via densi-
in fields by farmers to make their fields ready for the next fication. It offers several advantages, including (i) improved
crop.31,34 Incomplete combustion of rice straw liberates transport and handling efficiency, (ii) controlled particle
greenhouse gases and toxic pollutants which have been size distribution for improved feedstock uniformity and
reported to contributing to asthma and other respiratory compositional quality, (iii) compliance to predetermined
disorders in young children and the elderly.35 Rice straw conversion technology and supply system specifica-
burning also diminishes many soil nutrients (approxi- tions.38 Different equipments were evaluated for rice-straw
© 2017 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. (2017); DOI: 10.1002/bbb 3
Table 2. Habit and distribution of different species of rice.24

S.No. Species Habit Distribution
1 Oryza sativa Annual, cultivated South and Southeast Asia
2 O. nivara Annual, wild South and Southeast Asia
3 O. rufipogon Perennial, wild Tropical Asia, Australia
4 O. glaberrima Annual, cultivated Tropical West Africa
5 O. barthii Annual, wild Sub-Saharan Africa
6 O. longistaminata Perennial, wild Tropical West Africa
7 O. glumaepatula Perennial, wild Tropical West Africa
8 O. meridionalis Wild Tropical Australia
9 O. officinalis Perennial, wild South and Southeast Asia
10 O. minuta Perennial , wild The Philippines
11 O. rhizomatis Wild Sri Lanka
12 O. eichingeri Wild Sri Lanka, Tropical Africa
13 O. punctata Wild Tropical Africa
14 O. latifolia Wild Central and South America
15 O. alta Wild Central and South America
16 O. grandiglumis Wild South America
17 O. australiensis Wild Tropical Australia
18 O. granulata Wild Tropical Asia
19 O. meyeriana Wild Southeast Asia
20 O. longiglumis Wild Indonesia, Papua New Guinea
21 O. ridleyi Wild Southeast Asia, Papua New Guinea
22 O. schlechteri Wild Papua New Guinea
23 O. brachyantha Wild Tropical Africa
24 P. coarctata Perennial, wild South Asia
Table 3. Area, plant height, and yield of rice in different regions of the world.
Country Area (lakh hectare) Plant height (cm) Yield (ton/ha) References
25, 169, 170
United States 12.6 95–188 8.0
19, 24, 25
Thailand 109.6 100–600 3.1
25, 171, 172
Malaysia 6.0 63.1 3.0
24-27
China 298.8 36.2–48.3 6.6
24, 25, 173
Japan 16.2 102–117 6.5
24, 25, 29
India 418.5 90–130 3.3
19, 24, 25
Indonesia 128.8 — 5.6
19, 24, 25
Vietnam 74.4 — 5.4
19, 25
World 1583 — 4.1
densification like pellet mills, roller presses, piston presses, Rice straw structural constituents
cubers, briquette presses, screw extruders, tabletizers, and
and characteristics
agglomerators.38 The bulk densities of processed rice straw
are represented in Table 5 which showed approximately a Rice straw is recalcitrant in nature and its cell wall has
5- to 20-fold an increase in bulk density. been evolved to address several growing requirements,
Table 4. Major rice-producing continents/ 37.4 13.7 6.2 1.4

46.1
countries in the world.4
Continents /Countries Rice production
in (million tonnes)
World 758.9
Asia 686.4
China 210.1
India 165.3
Indonesia 74.2
Bangladesh 53.1
1029.6
Vietnam 44.0
Thailand 33.3 Asia Africa South America
Myanmar 28.3 North America Europe Australia
Philippines 18.6 Figure 1. Rice straw production (million tons) in different

Japan 10.7 continents.
Pakistan 10.3
Cambodia 9.7 Table 5. Bulk densities of various forms of
Korea Rep. of 5.5 processed rice straw.
Nepal 5.4 Form of processed Bulk densities, References
rice straw (Kg/m3)
Lao PDR 4.0 174
Loose 20–40
Malaysia 3.1 174
Chopped 40–80
Sri Lanka 3.0 19, 174
Baled 110–200
Africa 30.7 174
Moduled 96–128
Egypt 6.2 Hammer milled 40–100 174
Nigeria 5.3 Cubed 320–640 19, 174
Madagascar 3.5 Pelleted 560–720 174
Tanzania, United Rep. of 3.1

Mali 2.8
Table 6. Chemical composition of rice straw.
Guinea 2.2
Component Quantity (weight %*)
South America 24.9
Glucose 34.0–43.7
Brazil 11.9
Xylose 19.0–22.0
Colombia 2.6
Arabinose 2.0–3.6
Peru 3.1
Mannose 1.8–2.0
Northern America 9.1 Galactose 0.4
United states 9.1 Acid soluble lignin 2.2–6.0
Central America 2.9 Acid insoluble lignin 13.0–22.7
Europe 4.1 Ash and silica 7.8–20.3
European Union 2.9 Extractive (i.e., protein, pectin, wax and 16.1–19.3
Russian Federation 1.1 other nonstructural components)
Australia 0.9 * weight % was determined from recently published reports
11,39-41,43,44
including protection against harsh environmental condi- (i.e., xylose, arabinose), lignin (both acid soluble and
tions, insects, and pathogens. It is mainly composed of insoluble), ash, silica, and extractives (Table 6).11, 39-42
hexoses (i.e., glucose, galactose, mannose), pentoses Extractives (non-structural components) are mainly
Table 7. Ultimate analysis of rice straw from different countries.

Element (% w/w) United States Thailand Malaysia China India
H 5.2–5.5 4.1–5.6 4.8 6.1–6.3 6.7
C 36.0–41 30.2–38.7 38.8 47–52 38.8
O 36.3–38.0 36.40 35.5 38–45 38.8
N 0.6–0.8 0.4–1.2 0.5–0.7 <0.2 0.2
S 0.1–0.2 0.02 0.01–0.05 <0.1 0.2
Cl 0.4–0.6 n.d. 0.12 <0.02 n.d.
K 1.5–1.7 n.d. 1.4 0.04–0.05 1.3
19, 84, 175, 176 19, 177 85 86, 174, 175 29, 52, 84, 87
References
n.d.: not determined
by strong inter- and intra-chain hydrogen bonding to

Table 8. Proximate analysis of rice straw in
comparison to wheat straw and sugarcane form microfibrils. They provide mechanical strength to
bagasse. the plant cell wall and could be several micrometers long
Rice Wheat Sugarcane in rice straw and 12–35 nm in diameter.55,56 Hallac and
straw straw bagasse Ragauskas57 reported that degree of polymerization of
Proximate analysis rice straw (1820) is slightly higher than other agricultural
(weight %*) residues like wheat straw (1045) and bagasse (925) but it
Fixed carbon 11.3–16.1 15.9–17.7 7.0–13.4 is significantly lower than the hardwoods and soft woods
Volatile matter 35.0–72.4 65.5–79.0 42.2–82.2 (4000–5500). The degree of polymerization of cellulose
Ash and silica 7.8–20.3 5.2–10.5 0.9–11.0 or average glucose chain length has been found crucial
*weight % was determined from recently published
in determining the mechanical strength of cellulose
reports.47-53,178 fibers.2,58
Different approaches are being used to isolate and char-
acterize rice straw cellulose like combined chemical, enzy-
composed of proteins (about 3%) and pectins (about 2.8%) matic extraction, organosolv, and steam explosion. Fan
along with minor amounts of free sugars, chlorophyll, et al.59 evaluated the effect of alkali treatment (4% KOH)
fats, oils, and waxes.43,44 Ultimate/elemental analysis of with 2% H2O2 followed by inorganic acids (i.e., H2SO4,
rice straw from different regions of the world is shown HCl, and HNO3) or an organic acid (i.e., acetic acid) to
in Table 7. C, H, and O are the main components of bio- isolate cellulose from rice straw. It showed higher cellulose
mass having special relevance for gross calorific value. N yields in the presence of strong inorganic acids rather than
content is responsible for NOx formation responsible for acetic acid under identical conditions. A prolonged treat-
the main environmental impact factors of biomass com- ment for 6 h was required to achieve the same delignifica-
bustion. Cl and S are responsible for deposit formation tion efficiency (Table 9) with acetic acid.59 It has also been
and corrosion and are therefore relevant for high plant found that particle size of rice straw is also an important
availability. This data is also important for performing factor for the isolation of cellulose from rice straw. The cel-
the mass balances during biomass conversion processes lulose content increased with decreasing the particle size
and calculating the empirical molecular formulae.45,46 The until less than 0.18 mm and then it almost remained con-
proximate analysis of rice straw is compared with wheat stant with further particle size reduction (Table 10).59
straw and sugarcane bagasse (Table 8). It showed that ash Cellulose acetate is one of the most commercially impor-
and silica content of rice straw is significantly higher in tant cellulose derivatives. Depending upon its properties
comparison to wheat straw and sugarcane bagasse.47-54 it could be used for a variety of applications like fiber,
fi lm, paint, fi lter, and dialyzer. Cellulose acetate with a
Cellulose high degree of substitution has limited commercial appli-
cation due to its limited solubility in common organic
Cellulose is a linear polymer of D-glucose units inter- solvent. Therefore, different catalysts were used to obtain
linked with each other by β-1,4 bonds and held closely the desired degree of substitution and polymerization
Table 9. Comparison of acids in combination degree of polymerization. Arabinose/xylose ratio for rice
with alkali to isolate cellulose from rice straw.59 straw is approximately ~ 0.17 in comparison of 0.2 for
S.No. Acid Time (h) Cellulose content (wt %)
bagasse.39,60,63 Different methods were used to isolate and
characterize hemicellulose from lignocellulosic biomass
1 H2SO4 1 86
like hydrogen peroxide, alkali, alcohol, and a combination
2 HCl 1 85
of alcohol/alkali hydrolysis (Table 12). These procedures
3 HNO3 1 82
typically involve cleavage of ester linkages to liberate
4 CH3COOH 1 58 hemicelluloses from the lignocellulosic matrix followed by
5 CH3COOH 6 85 extraction into an aqueous media. Comparison of hemicel-
lulose extraction procedures suggested that alkali treatment
in the absence of H2O2 solubilized small molecular size
Table 10. Effect of particle size on the content of
cellulose isolated from rice straw.59 hemicelluloses, which were rich in glucose, probably origi-
nating from α-glucan, while the second-stage treatment by
S.No. Particle size (mm) Cellulose content (wt %)
alkaline peroxide-enhanced dissolution of larger molecular
1 >0.425 50
size hemicelluloses, rich in xylose, principally resulting
2 0.3–0.425 56 from L-arabino-(4-O-methyl-D-glucurono)-D-xylan.62 As
3 0.25–0.3 61 glucose is attached to hemicellulose side chains, it could be
4 0.25–0.212 68 easily extracted by mild treatment. It has also been found
5 0.18–0.212 76 that methanol and ethanol have similar hemicelluloses
6 0.15–0.18 83 solubilization capabilities. Two major monosaccharides in
7 <0.15 84 neutral alcohol soluble hemicellulosic fraction were xylose
(27–37%) and glucose (26–39%). However, alkaline ethanol
soluble fraction contained low glucose (8%) and high xylose
Table 11. Screening of catalysts for cellulose content (60%).181
acetylation and their effects on degree of
substitution, degree of polymerization and
yield.59 Lignin
S.No. Catalyst Yield Degree of Degree of
substitution polymerization Lignin is the second most abundant polymer on earth after
1 H2SO4 29.1 2.92 655
cellulose.64 Its characterization is essential to evaluate its
utility, strength, and integrity for subsequent downstream
2 HClO4 31.5 2.83 546
processing and applications. Nuclear magnetic resonance
3 H3PW12O40·6H2O 41.1 1.43 179
(NMR) spectroscopy emerged as a powerful tool for
detailed structural elucidation of lignin.64-66 One dimen-
(Table 11).59 It showed that lowest degree of polymeriza- sional (1D) proton (1H), carbon (13C) and phosphorus
tion and substitution was obtained with phosphotungstic (31P) NMR and two-dimensional (2D) heteronuclear single
acid acetylation catalyst. quantum coherence (HSQC) techniques have significantly
contributed to deciphering the structural and functional
Hemicellulose properties of lignin.67-74 1H NMR is used to determine the
quantity of different hydroxyl groups but polymeric nature
Hemicellulose is linked, in part, to lignin by covalent of lignin, proton diversity and irregularity of linkages
bonds, whereas the linkage between hemicelluloses and between lignin building units pose a challenge for signal
cellulose is via hydrogen bonding.60 Rice straw has low overlapping and data analysis. 75 13C NMR is widely used to
molecular weight hemicelluloses (weight average molecu- reveal the details of aryl ethers and condensed/uncondensed
lar weight 18 800–48 700 and number average molecular aromatic and aliphatic carbons but low sensitivity, long
weight of 8200–15 900) with degree of polymerization in acquisition time, and high sample requirement has limited
the range of 80 to 200.61 These are heterogeneous group its utility.75 31P NMR technique addressed the limitations
of polysaccharides with a high degree of polydispersity, of 1H and 13C NMR techniques and used effectively for
polydiversity, and polymolecularity.62 The degree of the quantitative determination of hydroxyl groups includ-
branching in hemicellulose is usually represented by the ing aliphatic, carboxylic, guaiacyl, syringyl, C5-substituted
arabinose/xylose ratio; the lower the ratio the higher the phenolic hydroxyls, and p–hydroxyphenyls in a relatively
short experimental time and with small sample size require-

Uronic acid (%) References
ments.71 The heteronuclear multidimensional correlation

179
180
181
181
181
181
181
181
62
62
NMR experiments further improved the sensitivity of 13C
nuclei by polarization transfer and by separating the over-
lapped signals. HSQC is the most frequently collected 2D
NMR spectrum that is used not only for structural identi-
2.5–5.63
fication but also for estimation of the relative abundance of
1.75
2.49
3.48
2.98
2.54
2.37
4.51
inter-unit linkages as well as S/G ratios in lignin. Although
this technique is not quantitative but it has been widely
n.d.
n.d.
employed to offer relative comparisons of inter-unit linkage

levels in biomass lignins, such as alfalfa, eucalyptus, poplar,
0.1–0.67
Galactose Mannose Rhamnose Fucose
wheat straw, and rice straw.65,75-78

0.09
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
Lignin is primarily composed of three types of monol-
ignols/hydroxycinnamyl alcohols (p- coumaryl, coniferyl,
0.36–0.85
and sinapyl alcohols) linked with each other by different

0.66
1.62
1.73
2.11
1.68
1.51
1.32
types of ether and carbon-carbon bonds like β-O-4, 4-O-

n.d.
n.d.
5, β-β, β-1 and β-5 to make phenylpropanoid units such

as p-hydroxyphenyl (H), guaiacyl (G) and syringyl (S).
1.83
2.12
1.62
1.74
1.98
0.80
Among these, the β-O-4 linkage is the most predominant

Table 12. Content of sugars and uronic acids of isolated hemicellulose from rice straw.
ether bond (about 40–60%) in rice straw lignin.64 Lignin is

n.d.
n.d.
n.d.
n.d.
proposed to be attached to carbohydrates by benzyl esters,

4.66–6.55
Sugars (%)
benzyl ethers and phenyl glycosides. Because of these

chemical linkages and tight physical bonding it is quite
7.77
17.17
16.21
15.05
15.42
15.61
7.48
6.2
n.d.
difficult to remove lignin in its native form.79,80 Lignin iso-

lated by different approaches is depicted in Table 13. These
26.87–53.42 11.75–16.93 24.58–54.37
Glucose
results show that soda and alcohol lignin of rice straw

have lower molecular weight in comparison to alkali and
53.06
29.82
28.19
26.51
39.39
26.39
8.17
enzyme lignin.80
57
21
Thermal and physiochemical properties of lignin largely

Arabinose
dependent upon type of biomass, S:G:H proportion,

11.15
15.29
15.58
14.93
12.27
15.94
18.10
molecular weight, degree of branching, isolation methods,

10
18
and purity. The S:G:H ratios of different bioresources are

compared in Table 14. It showed that sugarcane bagasse
Xylose
lignin has high S content in comparison to lowest in pine

27.27
31.78
32.69
36.80
26.96
36.21
59.62
lignin. Rice and wheat straw lignins contains about same

54.8
27
proportion of S and G units. Thermal gravimetric analysis

with derivative weight loss (DTG) and differential scan-
10% NaOH, 20 h + 50% acetic acid/95% etha-
ning calorimetry (DSC) are used to measure the thermal

0.25M NaOH, 2 h + ethanol precipitation at
1% NaOH, 2 h at 55°C + hydrogen peroxide
Ethanol (60%, 3 h) + 0.25M NaOH at 75°C

Ethanol (60%, 3 h) + 0.01 M HCl at 75°C
stability of different lignin samples (Table 15). Higher

Hemicellulose extraction conditions
nol precipitation at room temperature
enthalpy values of lignin from flax and alfalfa suggest

that more energy is required to break down the bonds in
these lignin compositions yielding a more stable and flame
Propanol (60%, 3 h) at 75°C
Methanol (60%, 3h) at 75°C
Butanol (60%, 3 h) at 75°C

Ethanol (60%, 3 h) at 75°C
retardant material in comparison of sugarcane bagasse,

(0.0–5.0%, 12 h) at 45°C
pine, wheat and rice straw lignin samples.81

1% NaOH, 2 h at 55°C
n.d. = not determined
Comparison of rice straw and lignin derived from it

by enzymatic extraction procedure has been evaluated
(Table 16).82 It showed that C, H and O content and energy
of lignin obtained from rice straw was higher than native
rice straw. Thus, lignin might prove to be a better feed-
55°C
stock to produce fuel by pyrolysis.
Table 13. Molecular weight distribution of rice straw lignin isolated by different approaches.80,182,183
Molecular weight distribution Alcohol lignin Alkali lignin Soda lignin Enzyme lignin* Regenerated enzyme lignin*
MN (g/mol) 1230–1420 4869–7263 805 4597 3957
MW (g/mol) 1250–1460 4962–20926 1069 8464 6835
MW/ MN 1.02–1.12 1.02–2.9 1.32 1.8 1.7

*Enzyme lignin was extracted from ball milled rice straw followed by enzymatic hydrolysis and while regenerated lignin was extracted after
dissolving the ball milled rice straw in 8% LiCl/DMSO followed by its regeneration in water and enzymatic hydrolysis.183
Table 14. S:G:H ratio of lignin in different biomass.60,184-186

Lignin aromatic units Rice straw Wheat straw Sugarcane bagasse Pine Flax Alfalfa Poplar Miscanthus
S 40 46 53.6–60 2 29 30 63 44
G 45 45 30.5–39.1 86 67 70 37 52
H 15 9 2–13.9 12 4 — — 4
S/G ratio 0.88 1.02 1.4–1.9 0.023 0.43 0.43 1.70 0.85
and poplar. Ferulic and p-coumaric acids were dominant

Table 15. Characteristics of lignin from different
biomass.186–190 hydroxycinnamic acids, which together comprised 59.2,
63.8, 68.1, 59.0, 73.3, 40.9, and 36.0% of the total phenolic
Feedstock Enthalpy (J/g) DTG (°C) Residue (%)
acids and aldehydes released from maize stems, wheat,
Rice straw 155 410 40
rice, barley, and rye straws, oil palm fiber, and poplar
Wheat straw 158 328 40
wood, respectively.
Sugarcane bagasse 67.9 413 7 A study carried out on different procedures to determine
Pine 133 336 29 the ester and ether-linked hydroxycinnamic acids of bio-
Flax 191 332 39 mass suggested that large amounts of ether-linked ferulic
Alfalfa 162 332 35 acid and p-coumaric acid are associated with lignin in the
cell wall.83 It was also found that predominant amount
of p-coumaric acid is ester-linked to lignin (55.8% in rice
Table 16. Ultimate analysis of rice straw and straw, 69.7% in wheat straw, , 69.4% in rye straw, 66.7%
lignin extracted from it by enzyme.82
in barley straw, 81.5% in maize stems, 86.7% in oil palm
Ultimate analysis (%, wt) Enzyme Rice straw fiber and 72.0% in poplar wood) whereas, about half of the
extracted lignin
ferulic acid is esterified to the hemicelluloses and/or lignin
C 50.42 40.24
(46.8% in wheat straw, 60.9% in rice straw, 54.1% in rye
H 6.24 5.44
straw, 57.6% in barley straw, 58.7% in maize stems, 62.5%
O 40.10 37.22 in oil palm fiber, and 54.1% in poplar wood), and another
N 0.35 3.40 half of the ferulic acid was etherified to lignin via phenolic
S 0.09 0.17 oxygen (Table 18).83
O/C 0.60 0.69
H/C 1.49 1.62
Role of silica and its effect on
Calorific value (MJ/Kg) 20.35 15.69
recalcitrance of rice straw
Empirical formula CH1.49O0.60 CH1.62N0.07O0.69
Rice straw and husk ash are two of the most common
Phenolic acids and aldehydes from rice straw were silica rice raw materials among agro residues. Its content
extracted by alkali treatment and compared with other and elemental composition may affect the choice of the
biomass like wheat, rye, and barley straws, maize stems, appropriate pre-treatment/combustion technology based
oil palm, and poplar (Table 17).83 It showed that rice straw, on melting behavior, deposit formation, corrosion, fly ash
wheat straw, maize stem contained higher amounts of emissions, logistics concerning ash storage, and utiliza-
phenolic acids and aldehydes than barley, rye, oil palm tion/disposal. Major ash forming elements are Si (75–91%)
Table 17. Phenolic acids and aldehydes (%, w/w) released by alkali treatment from rice, wheat, rye, barley
straws, maize stems, oil palm, and poplar.83
Phenolic acids and aldehydes Rice straw Wheat straw Rye straw Barley straw Maize stem Oil palm fiber Poplar
p-hydroxybenzoic acid 0.012 0.062 0.017 0.012 0.046 0.040 0.060
p-hydroxybenzaldehyde 0.081 0.061 0.013 0.031 0.19 0.011 0.080
vanillic acid 0.097 0.15 0.027 0.050 0.069 0.068 0.052
syringic acid 0.23 0.34 0.051 0.10 0.24 0.078 0.038
vanillin 0.13 0.34 0.12 0.24 0.30 0.078 0.11
syringaldehyde 0.12 0.28 0.10 0.18 0.39 0.13 0.12
acetovanillone 0.14 0.19 0.051 0.072 0.013 0.020 ND
p-coumaric acid 0.86 0.66 0.36 0.36 1.08 0.075 0.10
ferulic acid 0.87 1.24 0.68 0.66 0.75 0.24 0.17
sinapic acid ND ND ND 0.021 0.013 0.053 0.026
total 2.54 3.32 1.42 1.73 3.09 0.77 0.75
ND: not detectable
Table 18. Total ester and ether linked p-coumaric and ferulic acids content (%, w/w) in rice, wheat, rye,
barley straws, maize stems, oil palm and poplar extracted by different methods.83
Sample p-Coumaric acid Ferulic acid
a b a b
Total Ester-linked Ether-linked Total Ester-linked Ether-linked
c d c
I II I IId
b e d f b e
Rice straw 0.86 0.48 (0.23) 0.38 0.33 (0.22) 0.87 0.53 (0.10) 0.34 0.32 (0.17)f
d
Wheat straw 0.66 0.46 (0.22) 0.28 0.25 (0.18) 1.24 0.58 (0.11) 0.66 0.62 (0.25)
Rye straw 0.36 0.25 (0.11) 0.11 0.09 (0.05) 0.68 0.37 (0.08) 0.31 0.28 (0.14)
Barley straw 0.36 0.24 (0.11) 0.12 0.09 (0.06) 0.66 0.38 (0.07) 0.28 0.26 (0.14)
Maize stems 1.08 0.88 (0.39) 0.20 0.20 (0.11) 0.75 0.44 (0.08) 0.31 0.31 (0.15)
Oil palm 0.075 0.065 (0.030) 0.010 0.009 (0.005) 0.24 0.15 (0.04) 0.09 0.08 (0.03)
Poplar 0.10 0.072 (0.033) 0.028 0.026 (0.016) 0.17 0.092 (0.03) 0.078 0.068 (0.02)
a
Total contents of p-coumaric and ferulic acids were determined with 4 M NaOH at 170°C for 2 h.b Contents of total ester-linked p-cou-
maric and ferulic acids were determined by alkaline hydrolysis of dewaxed samples and alkali-soluble lignin fractions with 1 M aqueous
NaOH at 30°C for 18 h.c Contents of total ether-linked p-coumaric and ferulic acids were calculated as the difference between total and
ester-linked p-coumaric and ferulic acids.d Contents of total ether-linked p-coumaric and ferulic acids were determined by acid hydroly-
sis of the alkali-treated residues with dioxane/2 M HCl (9:1, v/v) at reflux for 1 h and acid hydrolysis of the dioxane-soluble lignin fractions
with dioxane/2 M HCl (9:1, v/v) at 87°C for 2 h.e Represents the content of esterified p-coumaric and ferulic acids in alkali- soluble lignin
preparations precipitated at pH 1.5; values were determined by alkaline hydrolysis of the lignin samples with 1 M aqueous NaOH at 30°C
for 18 h.f Represents the content of etherified p-coumaric and ferulic acids in dioxane-soluble lignin preparations precipitated at pH 1.5;
values were determined by acid hydrolysis of the lignin samples with dioxane/2 M HCl (9:1, v/v) at 87°C for 2 h.
followed by Ca, Mg, P, Al, Fe, K, Na, Ti (Table 19).84-88 In also contain silica but their content is usually low (0 to
addition, volatile elements such as Na, K, As, Cd, Hg, Pb, 4%).96,97
and Zn play a major role in gaseous phase from combus- Recent analytical research suggests that accurate determi-
tion and especially aerosol emissions. High silica accumu- nation of silica in ash from rice straw could be done through
lation in rice straw plays a vital role in improving growth, digestion in H2O2/HNO3/HF followed by complexation with
providing mechanical strength, reducing lodging, and H3BO3 and analysis by inductively coupled plasma optical
relieving the plant from biotic and abiotic stresses, pro- emission spectrometry (ICP-OES).98 Hydrofluoric acid was
tecting from pathogens and heavy metal toxicity.89-91,92,93-95 found to be important in this method as without it silicon
Straw from other crops such as oats, wheat and barley concentrations were lower than actual concentrations.98
Table 19. Elemental composition of ash of rice In rice, silica is polymerized preferentially in the epi-
straw from different countries. dermal cell wall, forming silica-cuticle double layers
Element (%) United States Malaysia China India
beneath the cuticle. This silica layer is thought to exert
various beneficial effects on the growth and development
Si 74.67 91 75.00 79.82
of plants. Rice plants treated with silica were found to
Mg 1.75 <0.01 1.90 7.54
reduce their lignin incorporation in cell walls.106 On the
Ca 3.01 3.21 1.50 0.370
other hand, deficiency of silica led to an increase in lignin
Fe 0.85 0.14 2.00 0.245 accumulation in rice shoots, most of which was guaiacyl-
Na 0.96 0.21 1.90 0.501 type lignin.107 In another study, although silica deficiency
Al 1.04 0.78 1.40 1.13 reduced rice plant rigidity, their sugar and lignin contents
Ti 0.09 0.02 0.02 n.d. were elevated as well as upregulation in carbohydrate and
S 1.24 0.72 0.9 n.d. lignin biosynthesis genes.108 In yet another study involv-
P 1.41 0.72 2.7 3.75 ing a low-silica mutant found silica to be distributed in
Reference 84 85 86 87 tissues important for maintaining rigidity of the plant.109
Recently, research studies indicated that much of the silica
n.d.: not determined
was fractionated along with Klason lignin, followed by
polysaccharides and lipids, in that order.110 Another article
Only the soluble form of silica as monosilicic acid suggested a functional correlation between mixed linked
[Si(OH)4] (orthosilicic acid) in soil can be transported by glucans (MLG) and silica. The MLG-deficient transgenic
rice plants.99 However, concentration of monosilicic acid rice line showed lower mechanical strength of leaf blade in
is low in soils (0.1 to 0.6 mM)100 making it an important comparison to the wild type.111
nutrient to ensure high productivity of rice considering its Silica may have a negative effect on cellulase
preference for high silica accumulation. Rice straw yields enzymes.112-115 A recent paper found nonproductive adsorp-
can be significantly impacted in soils with low soluble sil- tion of cellulase (Novozymes CTec2) to pure amorphous
ica content. Takahashi101 showed that dry weight of plant silica with a maximum enzyme binding capacity of 244 mg
per pot reduced from 32.3 to 22.4 grams when silica was per gram silica, and that adsorption increased with enzyme
lowered from 100 to 0 ppm, respectively. Evidence suggests concentration and temperature. In the enzymatic hydroly-
that monosilicic acid is likely taken up in rice plant by an sis of Avicel mixed with amorphous silica, they found that
active mechanism with energy acquired from aerobic res- addition of PEG1500 almost completely relieved inhibition
piration,92 and interestingly, only through lateral roots but caused by silica.116 High silica content of rice straw seems
not root hairs.102 Since the solubility of monosilicic acid to be a problem for biofuels and related products due to
is low, silica accumulation in high concentrations occurs buildup and wear on size reduction and extrusion equip-
through water loss during transpiration and allows its ment due to increase in shear stress.111 Desilication prior
polymerization to form amorphous silica (opal or phyto- to conversion process of biomass such as pre-treatment,
liths) (SiO2.nH2O) and deposition as incrustations largely enzymatic hydrolysis and fermentation might be required
in epidermis103 but also in vascular bundle, bundle sheath, to prevent scaling or fouling of equipment such as that seen
and sclerenchyma tissues.104 Scanning electron micro- in pulping processes.117 Moreover, biorefineries that burn
scopic images of epidermal layer in rice straw leaves are rice straw may cause microparticles of silica to be released
shown in Fig. 2. It showed silica in the form of cubic bod- in the air resulting in a health hazard unless electrostatic
ies, ladder like structures, trichomes (fi ne outgrowths or precipitators for capturing ash are employed.118 The fate of
appendages on plants), and stomas.105 Although the silica silica depends largely upon the type of pre-treatment and its
bodies seen in Fig. 2 appear to be randomly distributed conditions discussed in the following section.
in the epidermis of the rice plant, the distance between
adjacent bodies is almost constant and they occupy a 2D Pre-treatment of rice straw
triangular lattice in the xy plane of the epidermis. A plau-
sible explanation for high silica content in rice can be that Rice straw could be utilized for producing biofuels and
it can play the role of lignin in other plants as a compres- biopower through both biochemical and thermochemi-
sion-resistant component of cell walls as its incorporation cal platforms. For the biological platform, a pre-treatment
needs only 3.7 % and 6.7% of energy required for incorpo- stage is necessary to reduce rice straw recalcitrance by
rating lignin and carbohydrate, respectively.99,100 altering the interactions of cellulose, hemicellulose,
Figure 2. Scanning electron micrographs of epidermal cell surface of rice leaf. Arrow heads showed silica deposits on the leaf
surface (adapted with permission from (a) Talbot 212 and (b) Yamanaka 105).
Figure 3. Scanning electron micrographs of rice straw showing the morphology of surface before (a–c) and after pre-
treatment (d–f). Note: increase in micropores (arrows) after pre-treatment was observed (adapted with permission from Wi39).
and lignin; increase in cellulose accessibility; removal matic hydrolysis yields from biomass thereby increasing
of lignin-carbohydrates complexes; and/or reduction in the ethanol fermentation yields.60 Recent pre-treatment
cellulose crystallinity. These effects increase the enzy- approaches used for rice straw are summarized in Table 20
Table 20. Comparison of different pre-treatment conditions used for rice straw and their advantages/
disadvantages.
Pre-treatment Process conditions Proposed mode of Advantages Disadvantages References
action
11, 119, 121, 122,
Dilute acid 120–180°C, 0.25–1% • Hydronium ions break • Low chemical cost • Inhibitor formation
124, 125, 149,
of acid concentration, glycosidic linkages to • Applicable to multiple • Costly corrosive-
191, 192
5–10 min form monomeric sugars feedstocks resistant equipment
• Hemicellulose removal • High glucose yield
opens up pores • Recovery of monomeric
hemicellulosic sugars
• Less hemicellulase
enzyme required for
saccharification
120, 124, 127,
Alkali 120–140°C, 0.25– • Cleave lignin linkages • More effective with • Less efficient with high
129-131, 149, 193
0.5% of alkali con- and polysaccharide low lignin containing lignin biomass
centration, 10–20 min glycosidic bonds herbaceous crops and • High alkali costs
• Reduce degree of agricultural residues • Alteration of lignin
polymerization and • High lignin removal structure
crystallinity • Low inhibitor formation
• Fiber swelling and alka-
line saponification of
acetyl and uronic ester
bonds
136, 139, 194, 195
Steam 180–230°C, 10–30 • Sudden pressure • No chemical required • Energy and water
explosion bar, 10–20 min release disrupts bio- (environment friendly) intensive
mass structure and • High hemicellulose yield
defibrillates cellulose • Low inhibitor formation
bundles
140-142, 196
Organosolv 120–180 °C, • Hydrolyzes lignin and/ • High recovery of pure • High chemical costs
45–75% of solvent, or hemicelluloses lignin • Solvent recycling
30–90 min • Low inhibitor formation required
• High glucose yield • High volatility and
flammability
• Less environment
friendly
146, 148, 150,
Ionic liquid 70–150 °C, 100% of • Dissolve cellulose to • Highly amorphous cel- • High chemical cost
197-199
solvent concentra- reduce its crystallinity lulose recovered • Enzyme inhibitory
tion, 30–1440 min • Lignin removal • Less enzyme • Water intensive
requirement for • Solvent recycling
saccharification required
• mild reaction conditions
152, 153
Deep eutectic 60–120°C, • Lignin removal • Less enzyme • Water intensive
50–100% of sol- requirement for • Solvent recycling
vent concentration, saccharification required
660–1440 min • Natural biodegradable
chemicals
• Cost effective and
mild pre-treatment
conditions
along with process conditions, mode of action and advan- rough and porous surface with identifiable micropores.
tages/disadvantages. A pictorial glimpse of the rice straw The rougher surface and a higher surface area resulting
morphology before and after pre-treatment is depicted from the removal of hemicelluloses is generally linked to
in Fig. 2.39 It showed that pre-treated rice straw had a improved enzymatic hydrolysis.
Table 21. Physiochemical modifications during different pre-treatment methods for rice straw.
Rice straw Crystallinity FTIR peaks rearrangements Pore volume Enzymatic References
pre-treatment index (%) (m2/g ) saccharification (%)
125
Untreated 33.2–40.8 — 1.66–2.1 12–50
146 139
−1 125
Dilute acid 43–51.5 Peaks at 2900 and 910 cm enhanced while 2.5–5 71–85
1740, 1725, and 1245 cm−1 were diminished 121 124
120
-1 193 128
Alkali 40.4–60.4 Peaks at 3338 and 2918 cm reduced while n.d. 75.8–83.1
1358, 1427 1639 and 1718 cm-1 absent, new 129
peak at 1368 cm-1 appeared

Steam 49–51 Peak intensity at 1510 cm−1 enhanced while 5.8–6.6 61–90 136, 200 201
1060 cm−1 was reduced 139 8

134
135
−1 142, 143
Organosolv 54.5–58 Strong absorption peak at 1376 cm , peak at ~44–62
1745, 2920–2870 and 3327, cm−1 decreased
Ionic liquid 14–18.8 Peak intensities at 1055, 1162, and 1375 cm−1 n.d. 36–93 145, 150 202
reduced and peaks at 1250 and 1732 cm−1 absent

203 204
Deep eutectic 44.3–53 Reduction in peak intensities at wavelengths of Increase by 71–99
1244, 1514, 1720, 1734 cm-1 5.4-fold 152
n.d., not determined
Dilute acid pre-treatment (DAP) is one of the most popu- after DAP. The suggested reason for this effect was the
lar pre-treatment methods because of the low cost of sulfu- removal of hemicellulose and the opening of macropo-
ric acid and ability to perform well on multiple feedstocks. res which were about double in size with respect to the
X-ray diff raction (XRD) analysis showed that the crystal- untreated rice straw (Table 21).125 DAP has been reported
linity Index (CrI) of rice straw increased by about 10% after to keep much of the silica with pre-treated solids.103
DAP (Table 21) and the possible reason for this apparent Alkali pre-treatment (AP) is one of the most extensively
increase is the removal of amorphous hemicellulose and used approaches for low lignin containing herbaceous bio-
lignin and the subsequent enrichment in the concentra- mass and agricultural residues like rice straw.126 It removes
tion of crystalline cellulose.12, 119, 120 Fourier Transform most of the amorphous lignin and hemicelluloses from bio-
InfraRed (FTIR) spectroscopy analysis showed that peak mass at a relatively milder temperature but usually a longer
intensities for hemicelluloses were either reduced or duration than DAP is required thereby enhancing the rice
diminished after DAP but no change in the crystalline cel- straw CrI by 10–20% (Table 21). FTIR analysis indicated
lulose region was observed.74, 75,121 Teramura et al.122 found that removal and aromatic deformation of lignin along with
that ferulate NMR signals, representative of lignin-car- carbohydrate depolymerization (Table 21). 43,78,79,127 GPC
bohydrate linkage and other aliphatic linkages like 5-5/4- analysis showed that molecular weight and polydispersity
O-β (dibenzodioxin), β-O-4 (β-aryl ether), β-O-4-H/G index of rice straw lignin was reduced to 2320 g mol−1 and
(β-aryl ether p-hydroxyphenyl/guaiacyl), β-O-4-S (β-aryl 1.45, respectively, from 2910 g mol−1 and 1.87 present in
ether syringyl), and β-5 (phenylcoumaran) have decreased native rice straw after AP.124 Similarly, He et al.128 reported
substantially after DAP of rice straw. The reduction in that lignin polydispersity was reduced from 3.53 to 1.03
hemicellulose and arabinofuranoside NMR signals also along with its molecular weight after AP. The 1H NMR spec-
suggested that cross-bridges between lignin and carbohy- tra of lignin fractions extracted from native and pre-treated
drate were broken. Meng et al.123 found that smooth intact rice straw showed that the representative signals for Hα and
physical structure in SEM (scanning electron microscopy) Hβ of β-O-4 structures and Hγ of β-5 and β-β structures,
analysis of native rice straw was transformed to wart/ were removed after NaOH pre-treatment, indicating the
papillae type structure formed by deconstruction of cuticle cleavage of β-O-4, β-5, and β-β units.128 SEM micrographs
wax and silica layers after DAP. Sun et al.124 also, reported of the rice straw before and after AP pre-treatment showed
that cracks and separated fibrous structure were observed that the smooth, intact and ordered structure of native rice
straw gets modified into a rough and defibrillated mate- decreased significantly after organosolv. This was due to
rial.129 Elumalai et al.127 found that after AP, rice straw the solubilization of carbohydrate, lignin, and inhibi-
swelled and became spongy like material with high porosity tor formation. By increasing the severity factor from 2.0
and accessibility.130 Khaleghian et al.131 also suggested that to 4.3, the amount of solid recovery after pre-treatment
that the packed structure of native rice straw was opened decreased from about 85–88% to about half (49–58%).
up and outer silica layer was removed after pre-treatment Thus, a tradeoff is a needed between enzymatic digest-
which is believed to improve the enzyme accessibility. The ibility and the losses during pre-treatment. Recent report
extent of silica removal depends upon the alkalinity of the from Win et al.142 suggested that organosolv with ethanol
pre-treatment for example, 1% sodium hydroxide has been as a catalyst, enhanced the CrI of rice straw from 51% to
found to remove up to nearly 62.2% of silica in rice straw 58% at 210°C for 60 min (Table 21). FTIR analysis showed
while sodium carbonate was less effective.132,133 Alkaline the hydrolysis of lignin-carbohydrates linkages and lignin
conditions only transfer silica from biomass solids to pre- deacetylation.142,143 Zhang et al.144 suggested that a strong
treatment liquor, a part of which can be precipitated by low- absorption peak at 1376 cm−1 is representing the cleavage
ering the pH followed by filtration or centrifugation. of β–O–4 and α–O–4 linkages and accumulation of non-
During steam explosion (SE), biomass is impregnated etherified phenolic OH groups in lignin after organosolv
with high pressure steam followed by a sudden decompres- (Table 21). SEM analysis of organosolv pre-treated rice
sion that ruptures the plant cell wall making it amenable straw showed separated, exposed, ruptured fiber structure
for enzymatic hydrolysis. Usually SE is carried out at very with reduced outer bristles (2 to 3 μm) and pores in com-
high pressure and temperature with supplementation of parison to rigid, ordered, and smooth structure of native
catalysts like ammonia, acid, alkali, or oxidizing agents rice straw with 7 to 19 μm outer bristles. 40, 142
(i.e., hydrogen peroxide) may help in achieving high effi- Select ionic liquids (IL) are readily capable to dissolve
ciency at milder temperatures and pressures. 8,134,135 Zhou cellulose and/or remove lignin from the lignocellulosic
et al.136 showed a linear increase in rice straw CrI% (from biomass. The regenerated cellulose loses its crystallinity
38% to 49% and 51%) with increasing temperature (210°C and transformed to cellulose II having high enzymatic
and 220°C, respectively) this was attributed to the reduc- digestibility.142 A recent report by Gogoi and Hazarika145
tion in hemicellulose and lignin content (Table 21). FTIR found that 1-ethyl-3-methyl-imidazolium acetate ([EMIM]
showed that there was slight reduction in the band cor- OAc) is a potential IL for rice straw delignification. Chang
responding to C–O–C pyranose ring (found in lignin, cel- et al.146,147 found that efficiency of IL increases with
lulose and hemicelluloses).137,138 Degree of polymerization surfactants like sodium dodecyl sulfate (SDS) and cetyl
was reduced to 566 after SE in comparison of 1124 present trimethyl ammonium bromide (CTAB) and ultrasoni-
in native rice straw.138 SEM of native rice straw showed that cation. FTIR analysis of 1-butyl-3-methylimidazolium
the rigid and tight structure of native straw became frag- chloride [Bmim]Cl pre-treated rice straw showed that the
mented after SE.138 Wood et al.139 reported that SE at 210°C both lateral order index (LOI) (i.e., ratio of absorbance
is sufficient for achieving >90% of enzymatic saccharifica- of the peaks at 1437 and 899 cm−1) and the total crystal-
tion yields and any further increase in temperature (220°C linity index (TCI) (i.e., the ratio of the peak areas at 1373
or 230°C) did not improve the saccharification yields. and 2917 cm−1) have been reduced after pre-treatment
In organosolv pre-treatment, an organic solvent or its while intensities of amorphous cellulose increased (Table
aqueous mixture is used as catalyst under elevated tem- 21).148,149 XRD analysis showed that rice straw crystallin-
perature and pressure conditions. Aqueous mixtures of ity was reduced significantly from 62% (in native) to 14%
ethanol or acetone are two of the most popular organic after pre-treatment with [Emim] [OAc] (Table 21).145,150
solvents along with oxalic acid, citric acid, glycerol, and Thus IL improved enzymatic digestibility mainly by lignin
tetrahydrofuran. Based on the severity of organosolv pre- removal and reducing cellulose crystallinity. The SEM
treatment it can hydrolyze about 40–60% of the lignin analysis of ionic liquid pre-treated rice straw showed that
along with partial amount of hemicelluloses from rice the organized structure of rice straw was destroyed and
straw to produce cellulose rich pulp.140 Recently Asadi the cellulosic surfaces became rougher, more porous, and
and Zilouei141 optimized the organosolv pre-treatment agglomerated after pre-treatment.146, 148 Most of the silica
of rice straw for different temperatures, residence time present in the native rice straw was also removed by the IL
and ethanol concentration and found that although enzy- pre-treatment.
matic digestibility of pre-treated rice straw improved Deep Eutectic Solvents (DES) have recently gained inter-
by increasing the severity factor but the solid recovery est as green, cost effective, less inhibitory to enzymes/
fermentative microbes and as alternative to costly ILs.151 Table 22. Calorific value of rice straw from
These are made up of a hydrogen bond donor and acceptor different countries.
mixed together to form lower melting mixtures than their Country Calorific value, MJ/kg References
constituents. The research on biomass pre-treatment with 19, 84, 174
United States 11.5–15.3
DES is still in its nascent stages. 19, 177
Thailand 11.7–16.3
Kumar et al.152 suggested that hydroxyl groups of DES
85
Malaysia 15.1
interacted with hydrogen bonds of cellulose and make it
86
stable and unaffected during pre-treatment but it removed China 18
29, 52, 205
60% of lignin at mild temperature of 60°C and improved the India 12.3–28.5
enzymatic saccharification to 87%. Another recent report
suggested that choline chloride (ChCl) based DES specifi- ide or steam. Hydrogen was produced from rice straw by
cally remove lignin and do not affect cellulose like ChCl: lac- using a limestone catalyst, oxygen-rich steam as a gasifica-
tic acid removed >57% of rice straw lignin followed by ChCl: tion agent and microwave-assisted pyrolysis.160-164
malonic acid (52%) and ChCl: glycerol (37%).153 Hence, crys- Rice straw is also used as a fuel for boilers to produce
tallinity of the rice straw increases after DES pre-treatment power and earn carbon credits. Techno-economic analysis
(Table 21).154 Xu et al.154 reported pore volume of native rice showed that it is a viable option to generate mini-grid-
straw was also increased by 6 times after DES pre-treatment. based rural electricity in developing nations.165, 166 But
there are few bottlenecks like ash melting, snagging, super
heater choking, clinkerization, or a drop in boiler temper-
Thermochemical platform ature due to moisture in the bales. One approach is to mix
for rice straw and burn rice straw together with rice husks, wood chips,
and cotton waste to achieve the desired parameters.167
Pyrolysis is one of the most promising tools to produce Calorific value is an important index to represent the use-
bio-oil, biochar, and biogas from rice straw. The pyrolysis ful energy content of straw as a fuel. It is the quantity of
of rice straw in the presence of both nitrogen or hydrogen heat produced by its combustion at constant pressure and
at different temperatures (300–450°C) and pressures (1–40 under standard conditions. It is usually determined using a
bar) suggested that a higher bio-oil yield and conver- bomb calorimeter. Calorific values for rice straw from dif-
sion efficiency was achieved in the presence of nitrogen ferent countries are reported in Table 22. Rice straw from
under identical conditions.155 Rice straw bio-oil has been India has a broad range of calorific value (12.3–28.5) fol-
reported to be composed of a multitude of components lowed by Thailand and the USA (11.7–16.3 and 11.5–15.3).
including substituted ketones, aldehydes, carboxylic
acids, substituted phenols, furfural, and levoglucosan.156 Comparing rice straw and wheat
Biochar produced from rice straw can be used to improve straw for ethanol production
soil fertility, increasing carbon storage and decreasing
greenhouse gas emissions.157 It was found that controlling Rice and wheat are the two major food C3 crops around the
the pyrolysis temperature is more crucial than residence world providing almost two-thirds biomass yields of total
time to produce biochar.158 The yield, nutrient, volatile crop residues of the world.7 The high complexity of the plant
matter-content, cation exchange capacity and available cell wall structure and its interaction with various pre-treat-
potassium and phosphorus content of biochar get reduced ment methodologies have made it quite difficult to identify
with increasing pyrolysis temperature, alkalinity and key factors responsible for biomass recalcitrance and cor-
aromatic content. Rice-straw-derived biochar was further relate it with enzymatic digestibility. Recently, Wu et al.7
shown to absorb Cu(II) ion and cyromazine, an organic carried out a detailed study to evaluate the critical factors
insecticide.156 The downstream product from biochar gen- responsible for rice and wheat straw saccharification. It was
erated from slow pyrolysis of rice straw at 300°C has also observed that all rice mutants showed remarkably higher
been used to generate lubricants and greases. hexoses yields than that of wheat samples by 1.2–2.1-fold
Rice straw gasification for waste processing has recently after pre-treatment with three concentrations of NaOH and
gained interest to produce hydrogen and methane.159 H2SO4. It has also been found that three main wall-poly-
This process involves feedstock drying, pyrolysis, partial mer features, including cellulose CrI, non-KOH-extractable
combustion of intermediates and gasification in the pres- Xyl/Ara of hemicellulose, and KOH-extractable H/G of
ence of gasifying media, such as air, oxygen, carbon diox- lignin, rather than cell-wall composition (wall-polymer
Table 23. Comparison of rice straw and wheat straw for bioethanol production at high solid loadings.
Biomass Pre-treatment Saccharification Fermentation References
168
Rice straw Dilute acid pre-treatment 10% solid loading, enzyme con- Ethanol concentration was 23.23 g/L
with 4% (v/v) H2SO4 at centration of 9 FPU /g wheat straw (51.29% of maximum theoretical
121°C for 30 min reaction (crude cellulase from Aspergillus yield) with Kluyveromyces sp.), external sup-
time followed by alkali pre- terreus) plementation of β-glucosidase produced
treatment by using 0.5% ethanol concentration of 55.49 g/L (84.56%
NaOH at 121°C for 30 min of maximum theoretical ethanol yield)
and 20% solid loading
39
Rice straw Popping pre-treatment 15% solid loading, enzyme con- Ethanol concentration was 25.8 g/L (85.6%
at 220°C and 1.96 MPa centration of 23 FPU/g of rice straw of maximum theoretical
pressure (Celluclast 1.5 L, Novozyme and yield) with Saccharomyces cerevisiae
xylanase, Sigma) resulted in sugar
yield of 0.567 g/g
206
Rice straw Dilute acid pre-treatment 10% solid loading, enzyme concen- Ethanol concentration was 17.7 g/L (94% of
with 0.6% (v/v) H2SO4 at tration of 10% (v/w) of rice straw maximum theoretical
140°C for 90 min reac- resulted in 79% saccharification yield) with Kluyveromyces sp. IIPE453
tion time and 12.5% solid efficiency
loading
207
Rice straw Dilute acid pre-treatment 10.2% solid loading, enzyme con- Ethanol concentration was 21.5 g/L (77.3%
with 0.5% (v/v) H2SO4 at centration of 15 FPU/g of rice straw of maximum theoretical
170°C for 10 min reaction (Cellic CTec2, Novozyme) yield) with Saccharomyces cerevisiae KF7
time and 15% solid loading
208
Wheat Dilute acid pre-treatment 12.4 % solid loading, enzyme con- Ethanol concentration was 36.0 g/L with eth-
straw with 0.75% (v/v) H2SO4 at centration of 5.2 FPU/g of wheat anol yield of 0.29 g/g of wheat straw (86% of
160°C for 20 min reaction straw (Celluclast 1.5 L and Novozym the theoretical ethanol yield) at a productivity
time and 12% solid loading 188 from Brenntag Great Lakes, of 0.43 g/L/h with E. coli strain FBR5
Milwaukee, WI, USA)
209
Wheat Pre-treatment with H3PO4 20% solid loading, enzyme concen- Ethanol concentration was 71.2 g/L with
straw and H2O2 with 79.6% and tration of 20 mg protein/g cellulose ethanol yield of 0.112 g/g of wheat straw
1.9%, concentration, (about ~ 9.88 FPU/g cellulose) (Cellic with Saccharomyces cerevisiae (Angel Yeast
respectively at 40.2°C tem- CTec2, Novozyme) resulted in 77.4% Co., Ltd., Yichang, China)
perature and 2.9 h reaction glucan conversion
time and 10% solid loading
210
Wheat Steam explosion pre-treat- 10% solid loading, enzyme concen- Ethanol concentration was 25 g/L (86%
straw ment at 210°C temperature tration of 7.55 FPU/g wheat straw of the theoretical ethanol yield) with
and 6 min reaction time and (Cellic CTec2, Novozyme) resulted in Saccharomyces cerevisiae)
50% solid loading >90% glucan conversion
211
Wheat Steam explosion pre-treat- 11.7% solid loading, enzyme Ethanol concentration was 37.5 g/L with
straw ment with 1% (w/w) acetic concentration of 6.5 g Cellic ethanol yield of 0.32 g/g of wheat straw with
acid at 190°C temperature CTec3(about ~ 9 FPU/g solids) Saccharomyces. cerevisiae KE6-12b (Taurus
and 10 min reaction time (Novozymes A/S) Energy AB Lund, Sweden)
and 45-55% solid loading
168
Wheat Dilute acid pre-treatment 10% solid load solid loading with 9 Ethanol concentration was 18.29 g/L
straw with 4% (v/v) H2SO4 at FPU /g wheat straw by using crude (48.22% of maximum theoretical
121°C for 30 min reaction cellulase from Aspergillus terreus Yield) with Kluyveromyces sp.), external sup-
time followed by alkali pre- plementation of β-glucosidase produced
treatment by using 0.5% ethanol concentration of 38.19 g/L (72.47%
NaOH at 121°C for 30 min of maximum theoretical ethanol yield)
and 20% solid loading
levels), were predominant factors in biomass enzymatic or H monolignin proportion negatively affects CrI for high
digestibility upon various chemical pre-treatments. It has biomass saccharification.7 In one recent study, ethanol
also been indicated that either Ara degree of substitution produced from rice and wheat straw were compared under
the same pre-treatment, simultaneous saccharification and 2. Li F, Xie G, Huang J, Zhang R, Li Y, Zhang M et al., OsCESA9
fermentation conditions. These results showed that relatively conserved-site mutation leads to largely enhanced plant lodg-
ing resistance and biomass enzymatic saccharification by
high ethanol concentration was produced with rice straw reducing cellulose DP and crystallinity in rice. Plant Biotechnol
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23).168 Hence, this study suggested that rice straw can pro- 3. Fan C, Li Y, Hu Z, Hu H, Wang G, Li A et al., Ectopic expres-
duce higher bioethanol yields in comparison of wheat straw. sion of a novel OsExtensin-like gene consistently enhances
plant lodging resistance by regulating cell elongation and cell
However, further research is needed to compare both rice wall thickening in rice. Plant Biotechnol J n/a-n/a.
straw and wheat straw under identical conditions to deter- 4. Food and Agriculture Organization of the United Nations, Rice
mine which feedstock might provide higher ethanol yields. Market Monitor. FAO, Washington, DC (2017).
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but especially in Asia (>1000 million tons). But due to polymer features distinctive in wheat accessions and rice
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critical factors responsible for improved enzymatic digest- mentable sugar recovery at high solid loadings. Bioresour
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14. Agbagla-Dohnani A, NoziÈRe P, Gaillard-Martinie B, Puard M
All the financial and administrative support by Indian Oil and Doreau M, Effect of silica content on rice straw ruminal
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Bioenergy Award for Cutting Edge Research (BACER) to 15. Zhang J, Zou W, Li Y, Feng Y, Zhang H, Wu Z et al., Silica
distinctively affects cell wall features and lignocellulosic sac-
Dr Alok Satlewal from the Department of Biotechnology, charification with large enhancement on biomass production
Government of India and Indo-US Science and the in rice. Plant Sci 239:84–91 (2015).
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Dr Alok Satlewal Dr Parthapratim Das

Dr Alok Satlewal is working as a Re- Dr. Parthapratim Das is a postdoctoral
search Manager in the Department of researcher at the Chemical and Biomo-
Bioenergy, Indian Oil Corporation Ltd, lecular Engineering Department, Uni-
Faridabad, India after completing his PhD versity of Tennessee Knoxville, USA.
in Microbiology with a specialization in His research interests include system-
Molecular Biology and Genetic Engineer- atic development of inorganic catalysts
ing. He has about 10 years of industrial for energy storage and release and
experience and received first prestigious conversion of biomass to platform
Bioenergy Award for Cutting Edge Research conferred by chemicals and bio-renewable materials. He obtained
Department of Biotechnology, Government of India and his PhD in Chemistry from the University of Minnesota
the Indo-US Science and Technology Forum. He has also Twin Cities and worked at the Pacific Northwest National
worked in the Joint Institute for Biological Sciences, Bio- Laboratory.
sciences Division, Oak Ridge National Laboratory (ORNL),
Oak Ridge, USA and the Department of Chemical and
Biomolecular Engineering, University of Tennessee, USA.
Dr Ruchi Agrawal
Arthur J. Ragauskas
Dr Ruchi Agrawal is working as a
Arthur J. Ragauskas holds a Governor’s
Scientific Officer at DBT-IOC Centre for
Chair for Biorefining based in Univer-
Advanced Bioenergy, Indian Oil Corpo-
sity of Tennessee’s Department of
ration Ltd, Faridabad, India. She visited
Chemical and Biomolecular Engineer-
the Department of Chemical and
ing, with a complementary appoint-
Biomolecular Engineering, University
ment in the UT Institute of Agriculture’s
of Tennessee, USA and has expertise
Department of Forestry, Wildlife, and
in deconstruction and bioconversion
Fisheries and serves in the US Energy
of lignocellulosic biomass to ethanol, the scaling up of
and Environmental Sciences Directorate, Biosciences
biomass pretreatment, enzyme production, fermenta-
Division, at ORNL. He held the first Fulbright Chair in
tion, and downstream processing for second-generation
Alternative Energy and is a Fellow of American Associa-
bioethanol production. She did her PhD in Biochemistry
tion for the Advancement of Science, the International
with a specialization in Molecular Biology and Genetic
Academy of Wood Science and TAPPI. His research
Engineering and developed β-glucosidase hyper-produc-
program is directed at understanding and exploiting
ing mutants. She also worked on nanoparticles synthesis
innovative sustainable bioresources. Currently, he man-
for enzyme immobilization and developed biosensors for
ages a research group of graduate students, postdoc-
quick and reliable estimation of rhizobacteria during her
toral research fellows, a research scientist, and visiting
Masters in Biophysics.
scientists.
Dr Samarthya Bhagia
Dr. Samarthya Bhagia is a post-doc-
toral research associate in the Depart-
ment of Chemical and Biomolecular
Engineering at University of Tennes-
see, Knoxville. His current research
involves characterization of deuterated
plants for neutron scattering studies
in the Oak Ridge National Laboratory
(ORNL) Scientific Focus Area (SFA) Biofuels Program. He
holds a PhD in Chemical and Environmental Engineering
from the University of California, Riverside, and BTech
in Pharmaceutical Chemistry and Technology from
the Institute of Chemical Technology, Mumbai. He has
expertise in pre-treatment, enzymatic hydrolysis, and
characterization of lignocellulosic biomass.

Rice Straw As A Feedstock For Biofuels Availability, Recalcitrance, and Chemical Properties

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Rice Straw As A Feedstock For Biofuels Availability, Recalcitrance, and Chemical Properties

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Rice straw as a feedstock for

Keywords: rice straw; biofuel; biochemicals; biopower; recalcitrance; pre-treatment

Introduction generating enormous biomass residues, and it is also a

R duction because of its surplus availability around

ton in the United States and it is equal to 1000 kilo- Rice ecosystems

Table 1. Rice ecosystems around the world.19–21

Table 2. Habit and distribution of different species of rice.24

Table 4. Major rice-producing continents/ 37.4 13.7 6.2 1.4

Myanmar 28.3 North America Europe Australia

Philippines 18.6 Figure 1. Rice straw production (million tons) in different

Nigeria 5.3 Cubed 320–640 19, 174

Madagascar 3.5 Pelleted 560–720 174

Tanzania, United Rep. of 3.1

Table 7. Ultimate analysis of rice straw from different countries.

by strong inter- and intra-chain hydrogen bonding to

short experimental time and with small sample size require-

ments.71 The heteronuclear multidimensional correlation

employed to offer relative comparisons of inter-unit linkage

wheat straw, and rice straw.65,75-78

and sinapyl alcohols) linked with each other by different

types of ether and carbon-carbon bonds like β-O-4, 4-O-

5, β-β, β-1 and β-5 to make phenylpropanoid units such

Among these, the β-O-4 linkage is the most predominant

ether bond (about 40–60%) in rice straw lignin.64 Lignin is

proposed to be attached to carbohydrates by benzyl esters,

benzyl ethers and phenyl glycosides. Because of these

difficult to remove lignin in its native form.79,80 Lignin iso-

results show that soda and alcohol lignin of rice straw

Thermal and physiochemical properties of lignin largely

dependent upon type of biomass, S:G:H proportion,

molecular weight, degree of branching, isolation methods,

and purity. The S:G:H ratios of different bioresources are

lignin has high S content in comparison to lowest in pine

lignin. Rice and wheat straw lignins contains about same

proportion of S and G units. Thermal gravimetric analysis

ning calorimetry (DSC) are used to measure the thermal

1% NaOH, 2 h at 55°C + hydrogen peroxide

Ethanol (60%, 3 h) + 0.25M NaOH at 75°C

stability of different lignin samples (Table 15). Higher

nol precipitation at room temperature

enthalpy values of lignin from flax and alfalfa suggest

Butanol (60%, 3 h) at 75°C

retardant material in comparison of sugarcane bagasse,

pine, wheat and rice straw lignin samples.81

n.d. = not determined

Comparison of rice straw and lignin derived from it

stock to produce fuel by pyrolysis.

MW/ MN 1.02–1.12 1.02–2.9 1.32 1.8 1.7

Table 14. S:G:H ratio of lignin in different biomass.60,184-186

and poplar. Ferulic and p-coumaric acids were dominant

peak at 1368 cm-1 appeared

1060 cm−1 was reduced 139 8

reduced and peaks at 1250 and 1732 cm−1 absent

n.d., not determined

Dr Alok Satlewal Dr Parthapratim Das

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