pubs.acs.

org/journal/ascecg Perspective

Characterizing Variability in Lignocellulosic Biomass: A Review

Jipeng Yan, Oluwafemi Oyedeji, Juan H. Leal, Bryon S. Donohoe, Troy A. Semelsberger, Chenlin Li,
Amber N. Hoover, Erin Webb, Elizabeth A. Bose, Yining Zeng, C. Luke Williams, Kastli D. Schaller,
Ning Sun, Allison E. Ray,* and Deepti Tanjore*

Cite This: ACS Sustainable Chem. Eng. 2020, 8, 8059−8085 Read Online

ACCESS Metrics & More Article Recommendations

See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.
Downloaded via INDIAN INST OF TECH DELHI- IIT on August 1, 2021 at 03:59:40 (UTC).

ABSTRACT: Feedstock variability is a significant barrier to the scale-up and commercialization of lignocellulosic biofuel
technologies. Variability in feedstock characteristics and behavior creates numerous challenges to the biorefining industry by
affecting continuous operation and biofuels yields. Currently, feedstock variability is understood and explained largely on the basis of
chemical composition. Physical and mechanical properties and behavior of lignocellulosic feedstock in various unit operations,
studied through advanced analytical methods, can further explain variability. Such studies will enable us in developing processes and
designing equipment to improve operation and conversion performance. In this perspective, we review several advanced analytical
methods that measure density, moisture content, thermal properties, flowability, grindability, rheology properties, and
micromorphological characteristics. We also discuss the correlations and interactions among these properties that reflect the
complexity of lignocellulosic biomass as a feedstock and the associated quality metrics and logistics of supplying consistent quality
feedstock to a biorefinery. We also examine methods that have not traditionally been used to characterize lignocellulosic feedstocks
but have the potential to bridge the gap in our explanation of feedstock variability.
KEYWORDS: Feedstock variability, Biomass characterization, Physical and chemical properties, Operational reliability

■ INTRODUCTION
Biomass feedstocks, including energy crops, algae, municipal
waste, and industrial wet waste, as well as residues derived from
agriculture, forestry, and wood processing are important
sustainable energy resources. They can be directly or indirectly
converted to energy that powers our society. In 2017, wood and
wood waste provided 2% of the total U.S. annual energy
consumption, including fossil fuels, nuclear energy, and
renewable sources of energy. Also, biomass-based fuels
contributed to about 5% of the total primary U.S. energy.1 In
order to take full advantage of biomass resources available in the
U.S., a biorefinery should be able to accept feedstock grown in
wide-ranging geographical locations that experience substan-
tially varied growth-related conditions.2 Previous studies have
modeled biorefinery supply chains for system design to
minimize risk in biobased manufacturing.3,4 A comprehensive
understanding of the variability in feedstock supplied to a
biorefinery is also necessary to de-risk biobased manufacturing
as it will facilitate in developing technologies that can be tuned to
vary in intensity per feedstock being received at the biorefinery
gate. In this perspective, we review critical quality metrics,
current characterization techniques, and known impacts on
handling and conversion performance from varying physical
properties and chemical composition.5−10
Researchers have relied extensively on chemical composition
analysis of feedstocks as a tool to explain variability and develop
Received: October 20, 2019
Revised: February 17, 2020
Published: May 4, 2020

© 2020 American Chemical Society https://dx.doi.org/10.1021/acssuschemeng.9b06263

8059 ACS Sustainable Chem. Eng. 2020, 8, 8059−8085
ACS Sustainable Chemistry & Engineering
Figure 1. Volume definitions used for describing porous materials (refer to Tables 1 and 2 for the generally accepted terms and definitions for the
various types of density and volume encountered with porous materials). Figure adapted from Paul Webb.246
conversion technologies accordingly.11−15 Lignocellulosic bio-
mass mainly consists of three polymers: cellulose, hemicellulose,
lignin, and small fractions of protein and inorganic ash.
Concentrations of these polymeric components in the cell wall
structures of feedstocks vary based on many factors, including
type of feedstocks, growth environment, harvest time, harvest
and collection practice, material handling, and storage.7
Cellulose is a carbohydrate composed of linear chains of
thousands of β (1−4) glycoside-bonded glucose units. The
linear chains are arranged in parallel and connected via hydrogen
bonding forming a crystalline structure.16 Hemicellulose is
composed of five- and six-carbon sugars and has a highly
branched structure, which makes it more vulnerable to chemical
and enzymatic deconstruction. Lignin is a phenolic-based
polymer comprised primarily of three monolignol monomers
as precursors: p-coumaryl alcohol, coniferyl alcohol, and sinapyl
alcohol. Lignin bonds with cellulose and hemicellulose and
provides mechanical strength and chemical resistance to the cell
wall.7 The concentrations of these polymers in feedstocks are
currently, typically, studied by applying a series of chemical
fractionations and chromatography to the liquid phases.
High-pressure liquid chromatography (HPLC) is commonly
used to identify sugars and monomeric lignin against standards.
Mass spectrometry is applied when looking for molecules that
were unexpected and can help close mass balances. To
understand the solid-phase thermal degradation at increasing
temperatures, researchers commonly use thermogravimetric
analysis (TGA) by measuring mass loss as a function of
temperature and study the released gases with gas chromatog-
raphy (GC).7,17−19 Inverse gas chromatography (IGC) is used
to evaluate the surface energy of materials, which can explore the
impact of the apolar and polar forces that particle−particle
interactions have on materials handling.20,21
Spectroscopic techniques are calibrated with chemical
composition data from chromatography and other such
methods to rapidly test samples without material destruction.22
Hames et al.23 combined near-infrared (NIR) spectroscopy and
8060
pubs.acs.org/journal/ascecg Perspective
projection to latent structures (PLS) multivariate analysis to
rapidly analyze the composition of corn stover in a cost-efficient
manner. Li et al. used Raman spectroscopy methods to
characterize the variability of chemical composition in
eucalyptus, pine, and switchgrass by monitoring the identical
fingerprinting peaks for lignin with a classification of various
lignin structures. Their results identify the dominant units:
guaiacyl unit in pine, syringyl unit in eucalyptus, and both units
in switchgrass.24
Physical properties of feedstocks are also often studied to
define feedstock behavior. Light-based methods, including
Fourier transform infrared spectroscopy (FTIR)7 and micros-
copy have been used to study surface functional groups and
crystallinity and morphology of biomass, respectively.25 Jähn et
al.26 investigated the polymorphic transformation of the fine
cellulosic structure of flax fibers in vivo using FT Raman
spectroscopy. In Jähn et al.’s work, the microstructural fiber
properties were visualized by an environmental scanning
electron microscopy (ESEM).26 Kiemle et al.27 developed a
new monosaccharide quantification method using NMR
spectroscopy, which was also applied to lignin character-
ization.28 Surface texture is studied directly by a laser
profilometer,29 stereomicroscope,30,31 photographic scanner,32
or scanning electron microscope, which affects transport,
storage, conveyance, and physicochemical conversion.33 In
spite of the development of such intricate analytical methods,
explaining feedstock behavior during processing through the
various unit operations has been elusive, primarily due to a lack
of ability to explain feedstock variability by complementing and
correlating these properties.
Physical and chemical properties of biomass during
preprocessing and conversion vary not only with the unit
operations but also with variability in starting feedstock
materials.34 Feedstock characterization data generated by
many analytical methods can populate a comprehensive data
set that can be studied thoroughly for correlations and
interaction effects to identify the most informing measurements,
https://dx.doi.org/10.1021/acssuschemeng.9b06263
ACS Sustainable Chem. Eng. 2020, 8, 8059−8085
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Perspective

Table 1. Definitions and Terms Used in Describing Various Types of Volumes along with Volumes Included in Definitionsa
Volumes included in definitions
Solid Closed
material Open pore pore Interparticle External
Volume definitions volume volume volume void Volume void volume
Absolute powder volume (absolute volume): Volume of solid matter after exclusion of all √
spaces (pores and voids)b
Apparent particle volume: Total volume of the particle, excluding open pores but √ √
including closed poresb
Apparent powder volume: Total volume of solid matter including open and closed pores √ √ √ √
and intersticesb
Bulk volume: Volumes of solids in each piece, voids within pieces, and voids among pieces √ √ √ √ √
of the particular collectionc
Envelope volume: External volume of a particle, powder, or monolith such as would be √ √ √ √ √
obtained by tightly shrinking a film to contain itb
Sum of volumes of solid in each piece and voids within each piece, i.e., within close-fitting √ √ √ √
imaginary envelopes completely surrounding each piecec
Geometric volume: Volumes of a material calculated from measurements of its physical √ √ √ √ √
dimensions
Skeletal volume: Sum of volumes of solid material and closed (or blind) pores within √ √
piecesc
True volume: Volume excluding open and closed poresb √
Void: Space between particles in a bedb √
a
Table adapted from Paul Webb.246 bBritish Standards Institute (BSI).251 cAmerican Society for Testing and Materials (ASTM).252

Table 2. Definitions and Terms Used in Describing Densities along with Volumes Included in Definitionsa
Volumes included in definitions
Solid Open Closed External
material pore pore Interparticle void
Density definitions volume volume volume void volume volume
Absolute powder density: Mass of powder per unit of absolute volumeb √
Apparent particle density: Mass of a particle divided by its apparent (particle) volumeb √ √
Apparent powder density: Mass of a powder divided by its apparent volumeb √ √ √ √
Bulk density (bulk powder density): Apparent powder density under defined conditionsb
Mass of particles divided by the volume they occupy that includes the space between the particlesc √ √ √ √
Ratio of the mass of a collection of discrete pieces of solid material to the sum of the volumes of (1) the √ √ √ √
solid in each piece, (2) the voids within the pieces, and (3) the voids among the pieces of the particular
collectionc
Effective particle density: Mass of a particle divided by its volume included open and closed poresb √ √ √
Envelope density: Ratio of the mass of a particle to the sum of the volumes of the solid in each piece and √ √ √ √ √
the void within each piece, that is, within close-fitting imaginary envelopes completely surrounding
each piecec
Ratio of the mass of a particle to the envelope volume of the particleb √ √ √ √
Skeletal density: Ratio of the mass of discrete pieces of solid material to the sum of the volumes of the √ √
solid material in pieces and close (or blind) pores within piecesc
Tap density (tap powder density): Apparent powder density obtained under stated conditions of √ √ √
tappingb
Theoretical density: Ratio of the mass of a collection of discrete pieces of solid material to the sum of the √
volumes of said pieces, the solid material having an ideal regular arrangement at the atomic levelc
True density (true particle density): Mass of a particle divided by its volume, excluding open and closed √
poresb
a
Table adapted from Paul Webb.246 bBritish Standards Institute (BSI).251 cAmerican Society for Testing and Materials (ASTM).252

i.e., a function of measurements that can comprehensively
characterize feedstocks for their variability. In this perspective,
we closely reviewed many analytical methods developed to
measure physical, chemical, and biological properties of biomass
and commented on their individual aspects that may help
ascertain feedstock variability in its entirety.35
tion.36−38 The physical properties of lignocellulosic biomass
represent a broad array of attributes, including geometric and
volumetric (density and particle size, distribution, shape),39−41
thermal (heat capacity, conductivity, diffusivity),42,43 mechan-
ical (strength, compressibility, grindability, flowability),44,45 and
optical (color) properties.46

■ GEOMETRIC AND VOLUMETRIC PROPERTIES

The design and analysis of preprocessing and handling systems
for lignocellulosic biomass require extensive knowledge of
physical properties and the expected behavior of lignocellulosic
biomass. Such knowledge is used for capacity sizing, material
selection, logistic planning, and techno-economic evalua-
8061
Density. Density is an important material property in process
engineering applications and directly impacts the cost of
transportation and storage.47 Density is measured as the ratio
of mass to volume of material, and in the context of
lignocellulosic biomass, it is often categorized into bulk and
particle density.47,48 Biomass volume can also be categorized,
into particle volume, internal pore volume, and interparticle void
https://dx.doi.org/10.1021/acssuschemeng.9b06263
ACS Sustainable Chem. Eng. 2020, 8, 8059−8085
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Perspective

Table 3. Densities of Various Types of Lignocellulosic Biomass Feedstock at Different Condition

Bulk density (kg/m3)
True particle density
Biomass Descriptiona Loose Tapped (kg/m3) ref
Woody Aspen K.M; W.B.; M.C. = ∼9; d = 0.53 245 294 1335.1 Naimi et al.253
biomass Douglas fir K.M; W.B.; M.C. = ∼9; d = 0.60 343 396 1408.2 Naimi et al.253
Eucalyptus H.M; C.W.; M.C. = 0.1; d < 1 179.05 NA 1314.15 Goncalves et al.53
H.M; C.W.; M.C. = 0.2; d < 1 165.96 NA 1332.71 Goncalves et al.53
H.M; C.W.; M.C. = 0.3; d < 1 153.92 NA 1184.22 Goncalves et al.53
H.M; W.B.; M.C. = 0.1; d < 1 139.79 NA 1299.30 Goncalves et al.53
H.M; W.B.; M.C. = 0.2; d < 1 132.46 NA 1332.71 Goncalves et al.53
H.M; W.B.; M.C. = 0.3; d < 1 126.70 NA 1180.51 Goncalves et al.53
Loblolly pine H.M.; M.C. = 9.02; d = 0.776 267.1 342.6 NA Oyedeji and Fasina248
H.M.; M.C. = 4.78; d = 1.31 266.83 354.33 1459.30 Oginni58
H.M.; M.C. = 8.69; d = 1.31 275.53 359.67 1445.13 Oginni58
H.M.; M.C. = 16.53; d = 1.31 232.51 303.67 1444.10 Oginni58
H.M.; M.C. = 22.21; d = 1.31 227.36 303.67 1417.80 Oginni58
H.M.; M.C. = 25.53; d = 1.31 234.04 311.67 1387.50 Oginni58
H.M.; M.C. = 4.78; d = 0.50 205.02 264.67 1464.53 Oginni58
H.M.; M.C. = 4.78; d = 0.71 247.11 309.67 1462.93 Oginni58
H.M.; M.C. = 4.78; d = 1.00 265.30 323.67 1462.43 Oginni58
Norway spruce K.M., d = 0.44 187.85 293.78 NA Falk254
H.M., d = 0.26 175.29 281.25 NA Falk254
K.M., T.B.; d = 0.22 136.31 268.68 NA Falk254
H.M., T.B.; d = 0.19 94.67 176.81 NA Falk254
Poplar K.M; W.B.; M.C. = ∼9; d = 0.55 175 213 1461.5 Naimi et al.253
Southern yellow K.M; C.W.; d = 0.71 381.0 NA 1400 Phanphanich and
pine Mani46
K.M; C.W.; T.B.−225;d = 0.45 342.4 NA 1410 Phanphanich and
Mani46
K.M; C.W.; T.B.−250;d = 0.42 331.8 NA 1400 Phanphanich and
Mani46
K.M; C.W.; T.B.−275;d = 0.27 376.1 NA 1370 Phanphanich and
Mani46
K.M; C.W.; T.B.−300;d = 0.13 400.2 NA 1340 Phanphanich and
Mani46
K.M; L.R.; d = 0.74 351.3 NA 1350 Phanphanich and
Mani46
K.M; L.R.; T.B.−225; d = 0.57 351.7 NA 1390 Phanphanich and
Mani46
K.M; L.R.; T.B.−250; d = 0.53 336.6 NA 1370 Phanphanich and
Mani46
K.M; L.R.; T.B.−275; d = 0.46 331.5 NA 1340 Phanphanich and
Mani46
K.M; L.R.; T.B.−300; d = 0.36 330.5 NA 1330 Phanphanich and
Mani46
Willow K.M; M.C. = 8.5 ± 1.5; d = 0.53 291.06 NA 1415.64 Miao et al.40
K.M; M.C. = 8.5 ± 1.5; d = 0.75 239.86 NA 1441.90 Miao et al.40
K.M; M.C. = 8.5 ± 1.5; d = 1.55 192.46 NA 1470.06 Miao et al.40
K.M; M.C. = 8.5 ± 1.5; d = 2.12 168.76 NA 1411.35 Miao et al.40
K.M; M.C. = 8.5 ± 1.5; d = 3.16 156.43 NA 1374.59 Miao et al.40
K.M; M.C. = 8.5 ± 1.5; chips (25.4 × 25.4 400.09 NA NA Miao et al.40
× 38.0)
Herbaceous Alfalfa H.M; M.C. = 5.3; d = 0.34 238 NA 1232 Tabil and
Sokhansanj255
H.M; M.C. = 5.4; d = 0.36 263 NA 1300 Tabil and
Sokhansanj255
H.M; M.C. = 6.2; d = 0.38 236 NA 1287 Tabil and
Sokhansanj255
Barley straw H.M; M.C. = 13.5; d = 1.13 67.2 101 873.6 Tumuluru et al.256
H.M; M.C. < 12.4; d = 0.456 155 NA 1149 Adapa et al.257
Canola straw H.M; M.C. = 15.1; d = 0.98 80.4 119 1219.7 Tumuluru et al.256
H.M; M.C. < 13.4; d = 0.367 203 NA 1309 Adapa et al.257
Corn stover H.M; M.C. = 6.22; d = 0.41 131 NA 1170 Mani et al.236
H.M; M.C. = 6.22; d = 0.26 156 NA 1330 Mani et al.236
H.M; M.C. = 6.22; d = 0.19 158 NA 1340 Mani et al.236

8062 https://dx.doi.org/10.1021/acssuschemeng.9b06263
ACS Sustainable Chem. Eng. 2020, 8, 8059−8085
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Perspective

Table 3. continued
Bulk density (kg/m3)
True particle density
Biomass Descriptiona Loose Tapped (kg/m3) ref
K.M.; d = 3.26 66.56 80.24 NA Chevanan et al.258
K.M.; d = 12.79 34.44 38.35 NA Chevanan et al.258
Pellet 469.1− NA 529.2 − 808.1 Theerarattananoon et
624.6 al.54
Miscanthus K.M; M.C. = 8.5 ± 1.5; d = 0.37 255.03 NA 1413.95 Miao et al.40
K.M; M.C. = 8.5 ± 1.5; d = 0.46 213.32 NA 1413.47 Miao et al.40
K.M; M.C. = 8.5 ± 1.5; d = 0.56 166.86 NA 1374.81 Miao et al.40
K.M; M.C. = 8.5 ± 1.5; d = 0.73 148.85 NA 1285.55 Miao et al.40
K.M; M.C. = 8.5 ± 1.5; d = 1.29 114.72 NA 1260.25 Miao et al.40
Oat straw H.M; M.C. = 13.1; d = 1.50 58.3 90.6 839.3 Tumuluru et al.256
H.M; M.C. < 10.3; d = 0.404 196 NA 1240 Adapa et al.257
Reed canary grass K.M., d = 0.38 207.69 303.04 NA Falk254
H.M., d = 0.24 187.22 271.97 NA Falk254
Switchgrass H.M.; M.C. = 8.0; d = 0.46 115 NA 950 Mani et al.236
H.M.; M.C. = 8.0; d = 0.28 156 NA 1140 Mani et al.236
H.M.; M.C. = 8.0; d = 0.25 182 NA 1170 Mani et al.236
K.M.; M.C. = 8.5 ± 1.5; d = 0.41 237.97 NA 1428.16 Miao et al.40
K.M.; M.C. = 8.5 ± 1.5; d = 0.61 201.94 NA 1412.42 Miao et al.40
K.M.; M.C. = 8.5 ± 1.5; d = 0.85 148.85 NA 1434.84 Miao et al.40
K.M.; M.C. = 8.5 ± 1.5; d = 0.88 130.84 NA 1348.45 Miao et al.40
K.M.; M.C. = 8.5 ± 1.5; d = 1.37 94.81 NA 1254.41 Miao et al.40
K.M.; d = 3.30 105.18 135.68 NA Chevanan et al.258
K.M.; d = 12.32 45.26 51.63 NA Chevanan et al.258
Wheat straw H.M; M.C. = 9.5; d = 1.00 107 NA NA Adapa et al.257
H.M; M.C. = 9.5; d = 0.72 141 NA NA Adapa et al.257
H.M; M.C. = 8.6; d = 0.45 154 NA NA Adapa et al.257
H.M; S.E.; M.C. = 4.5; d = 0.57 41 NA NA Adapa et al.257
H.M; S.E.; M.C. = 4.7; d = 0.39 73 NA NA Adapa et al.257
H.M; S.E.; M.C. = 4.3; d = 0.31 100 NA NA Adapa et al.257
H.M; M.C. = 8.30; d = 0.64 97 NA 1030 Mani et al.236
H.M; M.C. = 8.30; d = 0.34 107 NA 1260 Mani et al.236
H.M; M.C. = 8.30; d = 0.28 121 NA 1340 Mani et al.236
H.M; M.C. = 15.6; d = 1.17 58.2 88.2 781.4 Tumuluru et al.256
K.M.; d = 3.35 50.46 62.75 NA Chevanan et al.258
K.M.; d = 12.27 25.06 27.68 NA Chevanan et al.258
Pellet 495.8− NA 613.3 − 852.0 Theerarattananoon et
649.2 al.54
a
C.W., clean wood without bark; W.B,: with bark; S.E,: steam-exploded; L.R, logging residues; T.B.−X, torrefied biomass at X °C; d, mean particle
diameter (mm); M.C,: moisture content of biomass (% w.b.); H.M., hammer milled; K.M., knife milled; NA, data not reported by author.

volume.6 The inclusion or exclusion of intraparticle and
interparticle pore volumes is the major difference between
bulk and particle densities. Figure 1 shows a pictorial
representation of the various volumes associated with porous
and granular materials that have been generally accepted in the
areas of catalysis and particle technology. The mass of a sample
or collection of granular materials is readily obtained; however,
the volume of a sample or collection of granular particles is not.
Most of the effort in measuring the density of material resides in
the precise and accurate measurement of the sample volume. For
example, if the volume measured is the skeletal volume (i.e., sum
of the solid material and closed pore volume), then the density is
referred to as skeletal density (Table 1). Care must be taken in
measuring sample mass due to confounding mass contributions
(e.g., moisture, fines). In general, mass measurement is
performed after a preconditioning step, designed to remove all
adsorbates that may affect the mass and volume measurements
(i.e., pore and bulk)adsorbates can also affect the measured
surface area. Bulk density takes interparticle pore volume into
8063
account, whereas particle density ignores it. The total volume of
biomass in a measurement mostly depends on sample handling
procedure; for instance, tapping and vibration of a container can
lead to a smaller volume and higher bulk density.49 The accepted
terms and definitions from the British Standards Institute and
the American Institute of Testing and Materials for volume and
density are listed in Table 1 (volume) and Table 2 (density).
Bulk Density. Low bulk density of biomass is an evident
challenge for collection, transportation, storage, and feeding to
operating units because it leads to large operating volumes and
thereby high cost.3,50 Freely settled and tapped bulk densities of
lignocellulosic biomass are two commonly measured variables.
More often, only freely settled (loose) bulk density is measured
and reported in the literature due to ease of measurement. The
use of bulk density is pervasive in process engineering models.
Tapped bulk density is an increased bulk density achieved after
mechanically tapping (raising and dropping) the material
containing vessel. Tapped bulk density simulates the maximum
attainable bulk density, without particle deformation.
https://dx.doi.org/10.1021/acssuschemeng.9b06263
ACS Sustainable Chem. Eng. 2020, 8, 8059−8085
ACS Sustainable Chemistry & Engineering
Bulk density of lignocellulosic biomass is relatively low
compared to other solid fuel resources such as coal, with woody
biomass typically having higher bulk density than agricultural
straws.51−53 Bulk densities of a few lignocellulosic feedstocks
from the literature are listed in Table 3. Loose bulk density
ranges from about 40 to 250 kg/m3 for agricultural straws and
from about 130 to 400 kg/m3 for woody biomass. Several
densification strategies, such as pelletizing, briquetting, and
baling, have been used to form lignocellulosic biomass into units
with increased bulk density, hence reducing the cost and
volumetric requirements for long-distance transportation,
storage, and handling. Pelletizing has been shown to increase
the loose density of agricultural straw by a factor of 3−5.54−56
Bulk density of lignocellulosic biomass is dependent on
particle size distribution, shape, and moisture content. Provided
that other factors remain the same, granular materials with larger
diameters tend to form bigger interparticle voids, hence possess
lower bulk density. Wider particle size distribution is expected to
produce higher bulk density because smaller particles can fill the
interparticle voids created by larger particles and form a denser
pack. Studies have also shown that a substantial portion of ash
contained in biomass ends up in the biomass fines fraction
during size fractionation.57,58 The implication of these studies is
that the bulk density of feedstocks increases with an increase in
the abundance of smaller particles, frequently ascribed to
reduced interparticle void and partially due to the elevated
amount of ash. Furthermore, an increase in the moisture content
of lignocellulosic biomass is accompanied by an increase in
particle size, causing a simultaneous change in its bulk density.
The change in bulk density is generally negative with increasing
moisture content if the bulk density is calculated on a dry basis.
However, on a wet basis, the associated change in bulk density
depends on the extent of particle size enlargement vis-à-vis mass
of additional water.56,59
Several institutions have established standard test methods for
loose bulk density measurement, including the American
Society for Testing and Materials: ASTM D1895-960 and
ASTM E873-8261 and the American Society of Agricultural and
Biological Engineers (ASABE S269.5).62
Envelope Density. Unlike bulk density, particle density is
defined as the mass of an individual or a group of particles per
the occupying volume that does not include the pore space
volume.63 Particle density is needed to evaluate the hydro-
dynamic behavior of biomass in drying, handling, and
fluidization applications. Since biomass particles are not simple
or consistently geometrical in shape, it is challenging to measure
volumes directly. Therefore, indirect methods have been
developed for particle density measurements. There are two
types of particle densities that are used to describe granular
materials, namely, true and apparent particle density. Where true
particle density is the ratio of particle mass to volume excluding
intraparticle and interparticle pores, apparent particle density is
the ratio of particle mass to volume including only intraparticle
pores. A summary of the literature on true particle density
measurement for some lignocellulosic biomass is provided in
Table 1. In the case of apparent density, ultrafine powder or
mercury is used as the displacement medium to envelop the
particles without filling intraparticle pores.64
True particle density is a convenient measure of stiffness of
lignocellulosic biomass and provides a beneficial outlook for
understanding grindability as well as other mechanical proper-
ties of lignocellulosic biomass.65 Apparent particle density is
commonly referred to as envelope density because its volume is
8064
pubs.acs.org/journal/ascecg Perspective
equivalent to the aerodynamic envelope around particles formed
by gas flowing past them.66 Therefore, apparent density is the
relevant particle density for fluidization, drying, sedimentation,
and pneumatic conveying of lignocellulosic biomass.66 Addi-
tionally, apparent particle density and loose bulk density of
biomass can be used to determine the amount of interparticle
porosity, which is the amount of interparticle void space relative
to the solid matter in bulk material (eq 1).
Porosity. Porosity is often a measure of the need for
densification before lignocellulosic biomass is transported
from the farm to the biorefinery.67 The higher the porosity is,
the more inefficient it renders transporting lignocellulosic
biomass without densification. Additionally, porosity is a reliable
measure of mean particle sphericity, as interparticle porosity is
inversely proportional to mean particle sphericity.68
ρloose
ϵ=1−
ρapparent (1)
where ϵ is the porosity of feedstock (−), and ρloose and ρapparent
are the loose bulk density (kg/m3) and apparent bulk density
(kg/m3), respectively.
Porosity can be assessed by studying adsorption isotherms
between a solid substrate and an adsorbent gas by first observing
the shape of the isotherm and selecting the best mathematical
description.69−71 A commonly used model for pore volume
evaluation is the Barrett−Joyner−Halenda (BJH) method.69,70
The theory is based on the Kelvin equation and does not account
for irregular shapes or nonrigid structures nor does it consider
micro/macropores.72 Considering that biomass has irregular
shapes, is nonrigid, and may often contain micro/macropores,
this model should be avoided. Without such limitations, the
Density Functional Theory (DFT) models are available that
allow for the selection of various parameters, such as material
type and geometry, and cover the entire range of pore size (nano,
micro, and milli).72 Porosity can be measured via several types of
techniques: electron microscopy,73 gas adsorption,72−76 and
mercury porosimetry on materials after drying.77−79 Porosity
can be also measured by solute exclusion on wet state materials80
and staining methods along with NMR techniques.73,81
Particle Size. Particle size and distribution have a great
impact on the physical properties of biomass.65,82 They affect
feedstock mixing, fluidization, surface area, heat and mass
transfer, and flowability.6 Accordingly, a strong correlation has
been observed between particle size and biochemical and
thermochemical conversion yields.83−88 Several techniques
including sieve analysis, image analysis, laser diffraction, and
sedimentation have been used to measure lignocellulosic
biomass particle size, with sieve analysis and image analysis
being the two most widely applied methods. Direct measure-
ment with calipers has also been reported in some cases when
the particles are observed to be especially large.59 Sieve analysis
is favored by researchers because it is relatively cheap and
versatile. Additionally, sieving is a characteristic feature of most
sorting and separation processes used in the biomass industry.
The drawbacks to this technique are that sieve selection can be
tedious and feedstock properties such as density, cohesiveness,
and adhesiveness, and shape may influence size classifica-
tion.89,90 Additionally, shaking may continually reorientate
particles in a manner that long particles with the small cross-
sectional areas may pass through aperture opening substantially
smaller than its length. Another limitation for this method is that
https://dx.doi.org/10.1021/acssuschemeng.9b06263
ACS Sustainable Chem. Eng. 2020, 8, 8059−8085
ACS Sustainable Chemistry & Engineering
the analysis results may be affected by the moisture content of
the ground biomass.91
Image analysis techniques involve the extraction of geometric
information from digital images of lignocellulosic biomass.
Typically, digital images are obtained using cameras, scanners,
or microscopes. This technique makes in-line measurement
possible so that dynamic process control can be implemented. A
key challenge of image analysis is that imaging equipment
typically can only capture two-dimensional projections instead
of three-dimensional objects.92 Hence, extensive preprocessing
and 3-D reconstruction of each particle has to be performed to
accurately obtain the geometric information for the third
dimension.93,94 Table 4 lists the differences between sieve
analysis and image analysis techniques.
Table 4. Comparison of Sieve Analysis with Image Analysis
for Particle Characterization64,92,259−261
Criterion Sieve analysis Image analysis
Cost Less expensive but laborious More expensive
Prevalence More common Less common
Dimension 1-D measurement 2-D or 3-D measurement
Measurement
base
Mass basis Volume or number basis
Shape No Yes
Measurement
Sampling Batch Batch and continuous
approach
Accuracy Sensitive to particle sphericity. Also, Less sensitive to particle
severe particle collision and sphericity and abrasion.
abrasion causing particle Sensitive to particle
fragmentation is common. aggregation.
Moisture Content. Moisture content of biomass refers to
the percentage of water mass in the total feedstock mass.
Moisture content of biomass can vary greatly. At harvest, the
moisture content of woody biomass is around 50%,95 while that
of agricutltural residues is typically about 20%.96 The amount of
water in biomass affects size reduction, drying, transport,
storage, processing, and physiochemical conversion for biofuels
or bio-oil.97 Most postharvest operations require moisture
contents to be below 20% for optimum performance.40,58,98
However, some studies have suggested a relationship between
increased water mobility in biomass microstructure and reduced
recalcitrance in downstream conversion processes, leaving
biorefineries with a difficult choice one way or the other.99
Biomass is in constant hydrodynamic interaction with its
environment. With changes in environmental factors such as
precipitation, humidity, wind, and temperature, biomass will
gain or lose moisture until reaching a relatively stable
equilibrium. Several moisture content determination ap-
proaches have been demonstrated in the literature for offline
and online applications, including oven drying, Karl Fischer
titration, toluene distillation, electrical capacitance tomography,
and near-infrared transmission.100,101 The oven drying method
following the ASABE standard S358.3 for moisture measure-
ment in forages is perhaps the most commonly reported method
for determining biomass moisture content.101 Factors, including
species, variety, maturity,102,103 porosity and microstructure,104
specific surface area,105 and amount of extractives and strength
of feedstock106 can affect the equilibrium status of biomass that
can be quantified as equilibrium moisture content (EMC).
There are two methods for EMC determination: static and
dynamic methods. In the static method, the experimental
humidities are obtained using a saturated salt solution in a closed
8065
pubs.acs.org/journal/ascecg Perspective
chamber. In the dynamic method, humidity is provided by
mixing fully dried air and fully saturated air. It is faster to achieve
equilibrium using the dynamic method than the static method.6
It is easier to maintain constant conditions in the static
method.107,108 The choice of analysis method depends on the
type and form of the feedstock. Static methods are preferable for
powdery materials, while the dynamic method is more practical
for pellets or briquettes.109
Micromorphology. The microstructure of biomass impacts
biomass processing and conversion kinetics (conversion
selectivity and yield), which ultimately dictates optimal
conditions for the economic viability of integrated biorefineries
(IBRs). Two of the most common and informative analytical
methods developed and employed for micromorphological
studies are field-emission scanning electron microscopy (FE-
SEM)110 and powder X-ray diffraction (PXRD)25,111 (Figure 2).
FE-SEM has a spatial resolution of less than one nanometer and
offers advanced performance at low accelerating voltages.112 FE-
SEM has been used as part of a set of microscopy tools to
investigate the impacts of different pretreatment reactor designs
on the micromorphology of biomass.113 FE-SEM has also been
used to analyze cellulose nanocrystals generated during ball
milling of biomass.110 PXRD is employed to explore the content
of microcrystalline cellulose (MCC), which affects the
progression of enzymatic hydrolysis of pretreated biomass.86,114
A higher crystallinity of biomass leads to higher recalcitrance to
enzymatic treatments. The overall crystallinity of biomass is
dependent on the wax and cellulose contents, as well as the
internal bonding among cellulose, hemicellulose, and lignin
polymers.115,116 Pretreatments change native crystalline struc-
ture of biomass, which increases accessibility to enzymes and
thereby improves sugar conversion kinetics. A linear relationship
between the crystallinity and carbohydrate conversion was
observed.86 Since all materials including the amorphous part of
cellulose, hemicellulose, and lignin can give rise to X-ray
scattering, it is necesssary to remove the wide unspecific peaks
and separate the amorphous from the crystalline part based on
the X-ray scattering. Different methods were developed to
calculate the crystallinity from XRD spectra, including the Segal
method,117 Ruland−Vonk method,118 Rietveld refinement
method,119 and Debye calculation method.120 XRD is usually
performed at 40 kV, an electric current of 30 mA, and a scan
angle from 10° to 80°, with copper as the radiant source. Studies
have shown that crystallinity increased because of the removal of
wax, lignin, and hemicellulose, which are more amorphous than
MCC.25,121
Surface Area. Increased accessible surface area of biomass
greatly impacts the efficiency of conversion processes.122−124
Surface area is impacted by biomass storage, size reduction, and
other processing methods. The kinetics of enzymatic hydrolysis
are impacted by accessibility and adsorption of enzymes to both
the cellulose and lignin surfaces.125
Surface area measurement can also be attained using data
from adsorption/desorption isotherms through a physisorption
process between a solid substrate and an adsorbent gas, such as
nitrogen, at temperatures low enough to condense the gas on the
material surface. Before physisorption takes place, the surface
must be prepared by drying or outgassing biomass either
through a flow-through gas system or by creating a vacuum
environment on the material at an elevated temperature that is
appropriately determined to facilitate the process without
significantly altering the surface. Surface area determination is
commonly carried out using the Brunauer−Emmett−Teller
https://dx.doi.org/10.1021/acssuschemeng.9b06263
ACS Sustainable Chem. Eng. 2020, 8, 8059−8085
ACS Sustainable Chemistry & Engineering
Figure 2. FE-SEM micrographs of biomass particle and cell wall
surfaces: (a,a′) control, (b,b′) ZC, (c,c′) SG, and (d,d′) HS. The left
column reinforces the particle size reduction and clumping seen at
lower resolution in the stereomicrographs. The right column shows
changes in surface roughness of the biomass cell walls caused by
pretreatment. Surface roughness measurements were calculated as the
standard deviation of grayscale values within six selected regions of
interest within three different SEM micrographs (orange square, inset).
(e) Mean standard deviation of the grayscale values and standard
deviation among the 18 surface roughness values are reported. HS,
horizontal screw; SEM, scanning electron microscopy; SG, steam gun;
ZC, ZipperClave. Reprinted from ref 143 with permission.
method (BET) in the relative pressure range of 0.05−0.3 or with
a single point at 0.3 relative pressure, measured as a ratio of
partial vapor pressure of adsorbate gas in equilibrium and
saturated pressure. When selecting the adsorptive, it is crucial to
consider the adsorptive properties of the probe gas in relation to
the chemical properties of the biomass surface. For instance,
functional groups existing on the surface of the substrate may
have specific interactions with nitrogen, due to the quadrupolar
nature of the nitrogen molecule, thus proving Ar or Kr to be
more suitable options.69
Energy Density. Process developers need to balance energy
consumption in biofuels production with the energy yield from
biomass. Energy density and energy yield from biomass can
affect the overall economic performance of plant design.126 Low
bulk density is a major problem for logistics operations because
8066
pubs.acs.org/journal/ascecg Perspective
of the corresponding low energy density leading to high
transportation cost.127 Energy density is also determined by the
composition of biomass including cellulose, hemicellulose,
lignin, extractives, and ash. Energy density is calculated by
heating value and bulk density in MJ/kg or BTU/lb.128 It can be
expressed in higher or lower heating valuewith or without
energy in water vapor, respectively. Higher heating values for
woody and agricultural residues range from 17 to 21 MJ/kg.129
To measure heating value, standardized biomass is burned in a
high-pressure oxygen cell that is immersed in a water bath. The
heat released from burning of biomass is absorbed by the water,
and the difference in water temperature is indicative of the
heating value. A strong correlation between energy density and
lignin and ash content of biomass was observed, especially in
pretreated solids.130 Accordingly, energy density changes along
with unit operations in a biorefinery process, sometimes with
time in the same unit operation due to loss of moisture. Real-
time energy density measurements, when correlated to chemical
composition or other properties, can inform us about the
progress of a biorefining processes with a particular biomass
treated through specific unit operations.
■ MECHANICAL PROPERTIES
Lignocellulosic biomass exhibits a variety of mechanical
properties, such as rheological properties, flowability, and
grindability. In biomass slurries with water, these properties
are primarily dependent on solids concentration. However,
feedstock variability can also impact these properties to a
significant level.
Rheological Properties. Rheological properties of pre-
treated biomass slurries, including yield stress and viscoelastic
properties, can be correlated with overall throughput, yield,
efficiency, and thereby processing costs. In general, materials are
classified into three categories: ideal solids (elastic), ideal fluids
(viscous), and viscoelastic. Biomass is viscoelastic,131 which
means it retains both elastic and viscous properties. The study of
viscoelastic properties of biomass before and after pretreatment
and enzymatic hydrolysis provides an indication of flow
behaviors. Rotational rheometers, torque rheometry, and
oscillatory rheometry are commonly used to explore the
viscoelastic properties, yield stress, viscosity curves, and
compliance of pretreated biomass.132−134 Capillary rheology is
used to characterize important physical phenomena, such as
liquid phase migration.134 Three interrelated parameters
elastic modulus, viscous modulus, and phase angleare
measured to study viscoelastic properties. When the phase
angle is higher than 45°, materials present liquid-like behavior
and vice versa.132 Typically, a high solids loading (less use of
water) reduces heating requirements and downstream product
dilution and thereby reduces processing cost.135−137 However,
increasing solids concentration also leads to high yield stresses
and viscosities,138,139 which introduces challenges in catalyst
mass transfer and biomass transfer from one treatment
operation to another.140−143 After pretreatment and enzymatic
hydrolysis, apparent viscosity decreases due to the reduction of
insoluble solids concentration.138,144
Thorough characterization of rheological properties will
benefit process development for feedstocks handling.134,145−147
Rheological properties are affected by feedstock types, chemical
composition, particle size distribution, porosity, fiber aspect
ratio, stiffness, additive type, solids concentration, and treatment
conditions.133,138,139,148 Hydrophilic polymers and larger
particles cause water sequestration in a solid phase, which
https://dx.doi.org/10.1021/acssuschemeng.9b06263
ACS Sustainable Chem. Eng. 2020, 8, 8059−8085
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Perspective

Figure 3. Relationship between Hausner ratio and flow index: loblolly pine,58,248 poultry litter,249 switchgrass,250 and pharmaceutical powder.s155
Note: Higher flow index indicates better flow behavior.247

leads to lower viscosities and yield stresses at the same solid granular flowability based on established empirical observations.
concentration and thereby better flowability.145 In poor-flowing granular materials, tapped bulk density is much
Flowability. In a successful biorefinery process, biomass greater than loose bulk density. Where the values of these two
needs to flow continuously and steadily from one unit operation bulk densities are similar in free-flowing granular materials, they
to another.149,150 Flowability is a property that describes are significantly different in lignocellulosic feedstocks. An
biomass feeding and transportation behavior, which is a crucial example of the relationship between flowability of particulate
parameter for biomass feeder and process design. 33,50 materials and the ratio of its tapped to lose bulk densities is
Flowability of biomass varies among species and is affected by presented by Bodhmage.155 Figure 3 shows the dependence of
factors, including biomass size, shape, density, moisture content, flowability, as measured by flow index, on the Hausner ratio for
cohesion, internal friction, yield stress, and compressibility.143 A loblolly pine, poultry litter, and switchgrass. Table 5 shows
failure of feeding or transferring of biomass can occur due to the
presence of oversized or fine particles, high moisture, or Table 5. Classification of Powder Flowability by Hausner
improper pressure control.143 There are four parameters Ratio and Compressibility262,263
commonly reported to characterize flowability of biomass: Hausner ratio (-) Compressibility (%) Flowability
compressibility index, angle of repose, cohesion coefficient, and 1.00−1.11 5−15 Excellent
flow index.151 Compressibility refers to the compacting 1.12−1.18 12−16 Good
propensity of biomass under forces. High compressibility of 1.19−1.25 18−21 Fair
biomass will lead to a poor flowability. The angle of repose is the 1.26−1.34 23− 28 Passable
steepest angle of a heap of biomass particles until falling.152 The 1.35−1.45 28−25 Poor
angle of repose together with particle diameter are used to 1.46−1.59 33−38 Very poor
calculate the cohesion coefficient, which depicts interparticle >1.60 >40 Extremely poor
frictional forces and wall friction.143,153 Flow index was studied
using the ratio of major principal stress to unconfined yield
stress.154 To measure the angle of repose, biomass is poured into
classification of powder flowability by the Hausner ratio and
a converging chute to form a semicone. The angle of repose (α)
compressibility.68
is calculated by the following equation: α = tan−1 ( h ), where h ρtap
r
and r are the height and the radius of the base of the semicone, H=
ρloose (2)

ij yz
respectively.

j z
C = 100jjj1 − loose zzz
A practical application of tapped bulk density is the estimation

jj ρtap zz
of bulk behavior of the material at the unloading site after ρ

compaction induced by vibration during transportation.61 It is
often used as a proxy indicator of flowability. With the
availability of information on loose bulk density, tapped bulk
density can be used to calculate a Hausner ratio (eq 2) and
compressibility (eq 3), which are frequently used to rank
8067
k {
(3)
where H is Hausner ratio (-), C is compressibility (%), and ρloose
and ρtap are the loose bulk density (kg/m3) and tapped bulk
density (kg/m3), respectively.
https://dx.doi.org/10.1021/acssuschemeng.9b06263
ACS Sustainable Chem. Eng. 2020, 8, 8059−8085
ACS Sustainable Chemistry & Engineering
Grindability. Biomass size is reduced through grinding to
facilitate biomass handling and transportation and improve
conversion efficiency. Grindability is the resistance of biomass
during grinding and is affected by biomass fiber length at the
microscale and the brittleness of biomass.156 A higher
grindability was achieved by increasing brittleness and reducing
the cellulose fiber length through torrefaction.46,157 Grinding
requires a large amount of energy depending on the particle size
(inlet and outlet), moisture content, feeding rate, and grinding
equipment configuration.156 Ten times less energy was required
to grind torrefied wood chips than the untreated materials in a
previous study.46 Although energy consumption in the grinding
process is high, it can significantly reduce the size of the biomass
and improve the kinetics of downstream processes of enzymatic
hydrolysis and fermentation.158 Mechanical milling decreases
the crystallinity of wood particles, reduces particle size, and
deconstructs cell wall structures to enhance enzyme accessi-
bility, thereby improving process efficiency and enzymatic
hydrolysis.159
Mechanical properties of lignocellulosic materials are relevant
in predicting biomass flow behavior in processes like grinding.
Mechanical properties vary with biomass chemical composition
and microstructure.160 Compression, tensile strength, and
bending tests are performed using load frames to understand
the elasticity and breaking strength of herbaceous and woody
biomass for many applications including agricultural161,162 and
bioenergy applications.163 At the submicrometer level, mechan-
ical properties of plant cell walls can also be measured using the
atomic force microscopy methods of nanoindentation and
quantitative force-volume mapping.164
A literature survey shows that the energy required to grind
lignocellulosic biomass can range from 1 to about 400 kWh/ton,
depending on moisture content, feedstock type, grinding
equipment, grinding extent, and feedstock pretreatment.165,166
Pretreatments such as fast-heat treatment, steam explosion, and
soaking in ionic liquids have been shown to drastically reduce
the diameter of resulting particles as well as the energy required
to grind.52,167,168 Size reduction equipment has also been
developed and evaluated by researchers, including the Forest
Concepts Laboratory crumbler169 and linear knife grid
system.170 Table 6 summarizes the major observations from
studies on lignocellulosic biomass grinding and outlines
parametric relationship between process variables and perform-
ance criteria, i.e., energy required to grind and particle size of
resulting grinds.
■
CHEMICAL PROPERTIES
Chemical Components. Determined by species and
growth conditions, chemical components of biomass directly
affect the conversion yield and process design.8,9 The most
commonly analyzed components are cellulose, hemicellulose,
lignin, extractives, ash, and trace elements. The National
Renewable Energy Laboratory (NREL)171 and Technical
Association of the Pulp and Paper Industry (TAPPI), as well
as ASTM International, developed standard methods for
biomass compositional analysis.172,173 An analytical pyrolysis
two-dimensional GC X GC-MS method was developed for cell
wall characterization.174 This method employed low temper-
ature (400 °C) analytical pyrolysis with 2D-GC-MS to detect
changes in biopolymer structure and chemistry in biologically
degraded corn stover. It revealed selective degradation of C5
sugars during biological degradation and heating that modifies
biomass composition and structural hemicellulose. Groenewold
8068
pubs.acs.org/journal/ascecg Perspective
et al. reported the application of the two-dimensional GC-MS
characterization on Miscanthus biomass in a pyrolysis process,
which provided a comprehensive understanding of the thermal
processing.175
The complex polymer network present in plant cell walls is
responsible for structural integrity, mechanical strength, and cell
function, representing a key factor in biomass recalci-
trance.176,177 Glycome profiling has emerged as a method to
characterize the cell wall architecture of biomass by employing a
diverse suite of antibodies to detect major noncellulosic
polysaccharides present in plant cell walls, such as hemi-
celluloses and pectins.178 Cell wall composition and structure
within a plant can vary across different tissues and anatomical
fractions179 for different levels of maturity and aging and in
response to environmental factors and growth conditions.180
Prior research has documented increased extractability of pectin
components in the cell walls of loblolly pine in response to low
soil moisture. In Pinus radiata, increased cell wall elasticity has
been observed under conditions of water stress and may be
attributed to drought tolerance.180,181 Stress-induced alterations
in cell wall elasticity are suggested to involve “cell wall loosening”
processes that result from rearrangements of structural cell wall
components, such as pectins and hemicelluloses. Increased
elasticity of plant cell walls in biomass may pose further
challenges to feeding, handling, and physical deconstruction of
biomass that are requisite for conversion to target intermediates
or products. Understanding how changes in the cell wall
structure, chemical components, and thereby mechanical
properties are imparted by a myriad of growth and production
factors is critical to informing how these attributes can be tuned
to improve bioprocessing of lignocellulosic feedstocks to
biofuels and coproducts.
Functional Groups Analysis. Analysis of functional groups
in cell structure can predict and evaluate process performance.
Analytic methods to study such functional groups in real time
include infrared spectroscopy (IR), NMR, and optical
microscopy. IR is a fast, simple, low cost, and nondestructive
method for the analysis of chemical components of biomass.
Along with other analytical methods, such as X-ray diffraction,
IR can lower the cost of measurement, increase the throughput,
and provide a better understanding of the biomass structure.22 It
is considered to complement Raman spectroscopy, since
vibrational modes that are Raman active are often weak in
infrared spectra and vice versa. The infrared portion of the
spectrum consists of three regions according to wavelength
range: near-infrared (780−2500 nm or 12800−4000 cm−1),
mid-infrared (2500−25,000 nm or 4000−400 cm−1), and far-
infrared (25,000−1000,000 nm or 400−10 cm−1).182 The near-
infrared and mid-infrared spectroscopy is usually developed for
qualitative and quantitative studies. Fourier transform infrared
spectroscopy (FTIR) is applied for studying the chemical
composition of wood and its changes during pro-
cesses.7,25,111,115,183,184 It can also be used to investigate
crystallinity and hydrogen bond formation. An in situ FTIR
microscopic cell was developed to monitor the structural
changes of plant walls during the process of enzymatic
treatment.185
The accuracy of the prediction depends on the population size
for the calibration. Recent studies reported that the combination
of NIR spectroscopy and projection to latent structures (PLS)
multivariate analysis can accelerate the speed of compositional
analysis with hundreds of samples per day at an 80−200 times
cost reduction compared to traditional wet chemistry
https://dx.doi.org/10.1021/acssuschemeng.9b06263
ACS Sustainable Chem. Eng. 2020, 8, 8059−8085
 Table 6. Review of Published Literature on Grinding of Lignocellulosic Biomass
ref Biomass Grinding equipment Variables tested Important observations
Oyedeji et Loblolly pine Hammer mill Moisture content, hammer mill Grindability was not significantly influenced by the length of storage.
al.264 screen size, and length of storage Grindability was inversely proportional to the moisture content of the feedstock.
Feedstock with higher moisture content produced grinds with lower bulk density.
Grinding may result in significant moisture loss.
Miao et al.40 Miscanthus, switchgrass, Hammer mill, knife Biomass type, grinding equipment, Hammer mill consumed less grinding energy than knife mill.
willow, and energy cane mill and moisture content Hammer mill produced grinds with larger particle diameter than knife mill.
Grindability of woody biomass (willow) was lower than the grindability of herbaceous biomass/agricultural
straw (Miscanthus, switchgrass).
Oyedeji and Loblolly pine Hammer mill Drying and grinding sequence Flowability of resulting grinds significantly increased with increasing moisture content of feedstock.
Fasina248 Alternated, multistage grinding, and drying of lignocellulosic biomass can be used to reduce overall energy
consumption and converse flowability of resulting grinds.
Mani et al.236 Wheat straw, barley straw, Hammer mill Moisture content and hammer mill Relationship between grinding energy and hammer mill screen size changes from linear (moisture content ≤
corn stover, and screen size 8%) to quadratic (moisture content = 12%).
switchgrass True particle density and loose bulk density of resulting grinds decreased with increasing hammer mill screen
ACS Sustainable Chemistry & Engineering

Adapa et al.52 Barley straw, canola straw,
oat straw, and wheat
straw
Naimi et al.265 Lodgepole pine wood
Naimi et al.266 Willow and Douglas fir
size.
Hammer mill Pretreatment (steam explosion), Except in the case of barley straw, steam explosion enhanced the grindability of feedstock.
hammer mill screen size, and Hammer milled feedstock produced nonuniform particle size distribution with right skewness.
biomass type
Grindability was biomass type specific.
Hammer mill Hammer mill screen size and Average particle diameter of the product was remarkably (75%−85%) lower than the aperture opening of the
diameter of feedstock installed screen.
Knife mill Knife mill screen size and diameter of Grindability of willow (hardwood) was lower than that of Douglas fir (softwood).
feedstock

8069
Bitra et Switchgrass, wheat straw, Knife mill Motor speed, knife mill screen size, Relationship between energy required to grind and knife mill motor speed was specific to the biomass type and
al.267,268 and corn stover feed rate, and biomass type knife mill screen size.
Total and no-load energy requirement increases with increasing motor speed.
Increasing feed rate generally reduced energy required to grind.
268
Bitra et al. Switchgrass, wheat straw, Hammer mill Hammer leading edge angle, motor Failure due to shearing was insignificant during hammer milling compared to that from impact/blunt force.
and corn stover speed, and biomass type Particle diameter resulting from hammer milling decreased with increasing motor speed.
Grinding energy had a concave relationship with the motor speed of hammer leading edge of 30°.
Relationship between energy required to grind was biomass type specific with hammer leading edge of 60°.
Brandt et al.167 Monterey pine Yellow Line A10 Pretreatment (ionic liquid soaking) Feedstocks soaked in ionic liquid typically resulted in smaller particle diameter compared to untreated feedstock
analytical grinder and were more grindable.
pubs.acs.org/journal/ascecg

Order of energy required to grind: Untreated > [C4C1m][HSO4] > Organosolv > DMSO > [C4C1m]
[MeCO2] > PFPE Fomblin Y 06/6 > Silcone oil > [C4C1m][MeCO2]80% > [C4C1m][HSO4]80% >
[C4C1m][NTf2].
Dooley et al.169 Douglas fir Crumbler Moisture content, veneer thickness, Crumbler technology produced low amount of fine during size reduction.
and shearing force orientation Energy required to grind was significantly lower for shearing parallel to grain compared to shearing cross grain.
Ghorbani et Alfalfa Hammer mill Hammer mill screen size and Significant quantities of moisture were lost during grinding.
al.269 diameter of feedstock
Himmel et Aspen, corn stover, corn Hammer mill, knife Grinding equipment type and screen Hammer mill consumed more energy during grinding but produced more fines compared to knife mill.
al.165 cobs, and wheat straw. mill, and attrition size and biomass type Attrition mills consumed most energy of the grinding equipment tested.
mill
Order of power consumption: aspen > corn cob > wheat straw.
Kokko et al.168 Sawed Scots pine Ultracentrifugal mill Pretreatment (torrefaction and the There is a convex relationship between anhydrous weight loss and grinding energy requirement.
fast heat treatment) Grindability of torrefied and fast heat-treated feedstock was similar.
Phanphanich Southern yellow pine chips Knife mill Pretreatment (torrefaction) Diameter of resulting grinds decreased with increasing torrefaction temperature.
Perspective

and Mani46 and logging There is a negative linear relationship between energy required to grind and torrefaction temperature.

ACS Sustainable Chem. Eng. 2020, 8, 8059−8085

https://dx.doi.org/10.1021/acssuschemeng.9b06263
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Perspective

methods.23 In the lumber and paper industies, NIR has been

used to investigate physical properties, such as density,
compression, and mechanical properties, as well as chemical
composition.186,187 NIR methods are also powerful tools for
Grindability of torrefied biomass increased with increasing torrefaction temperature and duration.

Energy required to grind increased with increasing size of material per batch and solids loading.
Diameter of resulting grinds decreased with increasing torrefaction temperature and duration.
Five minutes of torrefaction reduced grinding energy by more than 50%.
predicting other properties, such as moisture, ash, and char
content.188 Peak assignments from FTIR and NIR spectra are
summarized in Tables 7 and 8, respectively.
As a simple and reliable method, proton NMR (1H NMR) has
been used to quantify monosaccharides as well as degradation
products, such as acetic acid, formic acid, and HMF, obtained
from pretreatment.27,189 However, component peak overlaps

Diameter of resulting grinds was inversely proportional to motor speed.

were observed in the proton NMR spectroscopy, which makes it

difficult to quantify the amount accurately. Therefore,
Important observations

Energy required to grind increased with decreasing disk-plate gap.

Energy required to grind increased when motor speed was raised.

heteronuclear single quantum coherence (2D HSQC) was

developed for the monosaccharides and oligosaccharides to
overcome the issue of overlapping by applying the second
dimension.104 Carbon-13 nuclear magnetic resonance (13C
NMR) can be used to detect phenolic extractives and aromatic
compounds,87,115 which inhibit fermentation processes. Three-
dimensional NMR has been employed to study lignin
chemistry.190 Peak assignments from solid-state NMR are
summarized in Table 9.

■ INORGANIC SPECIES
Biomass feedstocks contain significant amounts of ash
constituents, which are composed of alkaline and alkali earth
metals, chlorine, sulfur, silica, and more. These inorganic species
originate from two main two types of ash forms: (1) introduced
ash from soil, rocks, and other forms of inorganic contamination
during the harvest and collection practices and (2) physiological
ash consisting of silica and various micro- and macro-nutrients
within the plant tissues and bound with cell wall polymers that
are naturally present through photosynthetic process.87,191
Disk-plate gap and solids loading

Depending on feedstock types, growing conditions, harvest

and collection practices, handling operations, and environ-
Pretreatment (torrefaction)
Variables tested

mental factors during harvest and collection, ash contents can

vary from less than 1% in debarked wood to as high as 25% in
herbaceous materials.192 These inorganic species can be
detrimental to feeding and preprocessing processes by
Motor speed

contributing to plugging and equipment wear and abrasion, as

well as reduced downstream conversion yields by deactivating
catalyst or increasing reactor slagging, fouling, and tar formation.
Fast and reliable analysis of inorganic species in lignocellulosic
biomass is important for understanding the source of variability
Grinding equipment
Ultracentrifugal mill

and quantifying the magnitude of their impact on preprocessing

and downstream conversion processes and thereby better design
Hammer mill

mitigation technologies to reduce and manage the variabil-

Disk mill

ity.193−198
Standard methods from the NREL biomass program,199 i.e.,
determination of ash in biomass, and proximate analysis with a
thermogravimetric analyzer as determined by the weight loss of
Miscanthus, corn stalks,

the ash measurement at 750 °C or the biomass standard

alfalfa, and willow

methods for ash in biomass (ASTM E1755-01) is often used to

Biomass
Beech and spruce

measure total ash and inorganic species. Current analytical

protocols to identify individual inorganic species include
inductively coupled plasma-optical emission spectrometry
Spruce
Table 6. continued

(ICP-OES, inductively coupled plasma-mass spectroscopy

(ICP-MS) and flame atomic absorption spectrometry (FAAS),
which generally require sample preparation and acid digestion
Zhu et al.271

Moiceanu et

methods. Laser-induced breakdown spectroscopy (LIBS) is an

Repellin et
ref

emerging nondestructive and rapid method that offers accurate

al.270

al.272

analytical results when compared with ICP-OES methods. The

LIBS method demonstrates a few advantages over the wet
8070 https://dx.doi.org/10.1021/acssuschemeng.9b06263
ACS Sustainable Chem. Eng. 2020, 8, 8059−8085
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Perspective

Table 7. Summary of FTIR Assignment of Peaks

Wavenumbers, cm−1 Assignment of peak Original compounds ref
800 and 1463, 1466 C−H and CH3 asymmetric scissoring deformations, aromatic 7
ring vibrations
843 aromatic C−H out of bending 273
990 C−O valence vibration Cellulose 274
1056, 1248, 1265, C−H and O−H bending frequencies Lignin 275,
1506, and 1603 276
1250−1270 O−C−O−C stretching vibrations Guaicyl lignin 7, 277
1125−1000 1042: C−O, C−C stretching, or C−OH bending in Xylan 275
hemicelluloses; 838, a-linkage; 903, β-linkage
1090−1045 OC−O−C stretching vibrations 7
1135, 1042 aromatic CH in-plain deformation for syringyl type and guaiacyl 273
type, respectively
1168 C−O−C vibrations in the anomeric region of hemicelluloses Arabinosyl side chains 275
870, 1263, 1506, and Lignin 183
1601
1606, 1513, 1426 aromatic skeleton vibrations 273
1638 carbonyl stretching conjugated with aromatic rings 278
1645 absorbed water 279
1730 keto tautomer β-diketones 7
1705 unconjugated ketone or carbonyl stretching 275
1742−1620 stretching mode of carbonyls mainly ketones and esters Mainly from waxes such as fatty acids, fatty esters, and high 7, 276
molecular mass aldehydes/ketones
1730 keto tautomer β-diketones 7
3370−3420 −OH stretching vibration Hemicellulose, cellulose, and lignin 7
2935−2915 CH2 and CH3 asymmetric and symmetric stretching vibrations 7,280

Table 8. Summary of NIR Assignment of Peaks particles and coupled with XRD to identify mineral species
present in extrinsic inorganic particles.209

Peak
location,
cm−1 Assignment of the peak
8700− Absorption bands corresponding to the second
8000 overtone of C−H stretching vibrations
5988− First overtone C−H stretching bands
5813
6990 First overtone of O−H (stretching)
chemistry methods, including little sample preparation, no
reagent consumption, and instantaneous generation of mean-
ingful analytical data.200
Other analytical methods were developed to produce real-
time observation of inorganic species to improve online process
control including near-infrared (NIR) spectroscopy201 and X-
ray fluorescence (XRF) spectrometry.202 A recently reported
advanced approach can differentiate between exogenous and
naturally embedded ash in lignocellulosic biomass samples by
combining energy-dispersive XRF and NIR spectroscopy. These
results open up new routes and instrumentation that can
monitor and control varying ash mass fractions better in
biobased feedstocks entering biorefinery processes.203 NIR is
also a powerful tool for predicting other properties, such as
moisture, ash, and char content.188 NIR, however, has
limitations for predictions of ash, because it only measures
inorganics that are organically bonded.188,204−208 Coupling NIR
with other spectroscopic methods has been shown to generate
more robust calibrations.203 A recent study highlights the
application of a composition-preserving extraction and charac-
terization method to distinguish between intrinsic and extrinsic,
soil-accumulated inorganic species that are associated with
biomass. Traditional ICP with atomic emission spectroscopy is
used for total elemental analysis, while SEM-EDS was used to
analyze the composition of extracted, extrinsic inorganic
■
ref OTHER FEATURED ANALYTICAL TECHNIQUES
7 Optical Microscopic Characterization of Chemical
Composition. Optical microscopy is an efficient tool to obtain
7 spectroscopic information from a broad region of interest that
281,282
can range from several hundred nanometers to several hundred
micrometers in size. Tissue- and cell-specific microscopic
chemical analyses are useful complements to the ensemble
chemical compositional analysis that provides the overall
composition of the bulk material. The regions that are critical
to specific physical properties, often the surfaces or interfaces,
may (1) constitute only a small fraction of the bulk material and
their signals could be overwhelmed by the ensemble measure-
ment for the whole material, and (2) their chemical
compositions might be different from the bulk material and
cannot be accurately represented by the ensemble measure-
ments. In addition, optical spectroscopic measurements can
provide rapid characterization of both chemical composition
with specific localization and morphology.
The physical properties of biomass feedstocks emerge from
their underlying macromolecular interactions, which can
undergo substantial changes across multiple length scales during
the harvest, storage, and preprocessing and conversion
processes: (1) At the subnanometer level, the functional groups
on carbohydrates and lignin can be significantly modified during
storage and pretreatment. For example, oxidation and microbial
degradation during storage can produce more C−O groups on
carbohydrate surfaces.210 (2) At the macromolecule level, the
bond formation and cleavage taking place during storage, and
preprocessing can cause condensation of the macromolecules.
For example, lignin tends to migrate and condense when the
attached hemicellulose is removed by dilute acid pretreat-
ment. 211 (3) At the micrometer scale, the modified
intermacromolecular interactions will change the overall three-
8071 https://dx.doi.org/10.1021/acssuschemeng.9b06263
ACS Sustainable Chem. Eng. 2020, 8, 8059−8085
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Perspective

Table 9. Assignment of Peaks of Lignin in Solid-State spectroscopy can overcover the background noise from water.
NMR275,283−286 Therefore, they are especially suitable for the analysis of
biological samples. Also, FT Raman can observe the
Signal location,
ppm Assigned compounds conformation-sensitive low-frequency region, which is hardly
observed in the infrared spectra. Fluorescence-based micros-
57−103 Polysaccharides: 81.6, C-4, 4-O-MeGlcA; 80.2, C-4, Glc
internal unit copy detects the distribution and interaction of fluorophores,
168.1 C-γ in etherified ferulic acid usually lignin. While confocal Raman often suffers from the
160 C-4 in esterified p-coumaric acid native fluorescence background, nonlinear Raman-based chem-
104.4−152.3 Aromatic part of lignin ical imaging techniques, particularly stimulated Raman scatter-
149.8 and 149.2 C-3 in etherified guaiacyl units ing (SRS), and coherent anti-Stokes Raman scattering (CARS)
148 and 147.1 C-4 in etherified guaiacyl units; C-3/C-5 in nonetherified provide faster mapping of the functional groups in plant
syringyl units tissues.217,218 The coherent Raman signal generated by these
145.4 C-4 in nonetherified guaiacyl units nonlinear processes is much higher than traditional confocal
144.6 C-a in esterified p-coumaric acid Raman and allows for efficient mapping of chemical function
144.3 C-a in etherified ferulic acid groups by SRS/CARS and has become a useful approach for
138 C-4 in etherified syringyl units visualizing the chemical functionality of plant cell walls during
135 C-1 in etherified guaiacyl units; C-1 in etherified syringyl biomass conversion.219 For example, Figure 4 shows images of
units
cellulose, hemicellulose, and lignin components in corn stover
132.8 C-1 in nonetherified guaiacyl units; C-1 in nonetherified
syringyl units during progressive digestion by hemicellulases.220 While
130.2 C-2/C-6 in esterified p-coumaric acid cellulose and lignin are indeed unaltered in a 2D image (<300
125.4 C-1 in esterified p-coumaric acid nm resolution), the 3D imaging of hemicellulose reveals the
122.4 and 122.9 C-6 in etherified ferulic acid diffusive digestion pattern of hemicellulose during enzyme
119.5 C-6 in guaiacyl units digestion (Figure 5).220
115.9 and 115.4 C-3/C-5 in esterified p-coumaric acid Confocal fluorescence microscopy with variable excitation
114.6 C-5 in guaiacyl units and emission wavelength selection provides useful information
111.2 C-2 in guaiacyl units about the fluorophores in biomass and feedstock. In addition to
152.3 C-3/C-5 in syringyl units fluorescence intensity, fluorescence lifetime imaging microscopy
104.4 C-2/C-6 in syringyl units (FLIM) provides the lifetime decay rate of the fluorophore,
86.1, 72.4, 60.1 β-O-aryl ether structure in lignin preparation providing an extra dimension of information to reveal the
86.1 C-β in β-O-4 interactions of fluorophores and the imaging environment. Zeng
72.4 C-a in β-O-4 et al.221 discovered that the lignin-enriched residues remaining
71.9 C-γ in β-β after acid pretreatment of biomass exhibit much shorter lifetimes
60.1 C-γ in β-O-4 than lignin in native in cell walls, while lignin in lignin
56 OCH3 in syringyl and guaiacyl units carbohydrate complexes showed longer lifetimes.
14−33.8 γ-methyl, α- and β-methylene groups in n-propyl side Surface Energy. The impact of surface energy has been
chains of lignin overlooked in biomass solids processing and handling. Surface
104.7 C-1 of the β-D-Xylp units energy is a variable that is widely used throughout industries
78.6 C-4 of the β-D-Xylp units such as coatings, pharmaceuticals, catalyst manufacturing,
77.1 C-3 of the β-D-Xylp units membranes, polymers, and adhesive industries.222 Surface
75.6 C-2 of the β-D-Xylp units energy characterization of solid surfaces has successfully played
65.9 C-5 of the β-D-Xylp units a role in optimizing paint formulations, powder flowability,
111.8, 88.5, 83, C-1, C-4, C-2, C-3, and C-5 of a-L-arabinofuranosyl adhesives, and particle agglomeration.223
80.8, and 64.1 residues linked to β-D-xylans, respectively
Surface free energy (γs) is the energy needed to create one unit
area of the new surface.224 Total surface energy (γts), indicated as
dimensional structure of the macromolecules. For example, mJ/m2, is the additive result of the dispersive (apolar) (γds ) and
removing and relocalizing lignin away from the cellulose will acid−base (polar) (γab s ) interactions. It is understood that the
lead to more exposed carbohydrate surfaces and generate more forces governing particle−particle interactions of materials are
accessible sites for enhanced enzyme digestibility.212 On the responsible for adhesion, cohesion, wettability. These factors, in
other hand, removing nearly all the cell wall matrix polymers will addition to roughness, porosity, surface area, moisture content,
lead to a denser packing of the cellulose microfibers and result in aspect ratio, and particle size can greatly influence flowability,
more recalcitrance for conversion.213 Disrupting the hemi- which is one of the bulk solids processing chal-
cellulose−cellulose−lignin network will lead to a redistribution lenges.69,72,122−124,222,224−233
of lignin to form separated lignin−carbohydrate globules.211,214 Inverse gas chromatography (IGC) is an analytical method
Two types of optical microscopy, Raman and fluorescence used to evaluate the surface energy of materials with irregular
lifetime imaging microscopy (FLIM), are particularly useful in surfaces, such as milled biomass, where traditional methods such
characterizing the above changes in biomass. Raman-based as contact angle (CA) would not be applicable. The technique
microscopy reveals the distribution of functional groups or was developed out of necessity to evaluate low vapor pressure
chemical species identified by corresponding function groups. materials such as polymers that could not be introduced into a
Fourier transform (FT) Raman spectroscopy was developed as a capillary column as a vapor. The term “inverse” in IGC refers to
quick and easy method to detect the major chemical the way that it differs from conventional gas chromatography. In
components of plants in vivo215 and track the molecular IGC, the mobile phase is swapped out with the stationary
changes during growth14 and thermochemical treatments.216 phasemost equipment is outfitted with a TCD or FID
Compared with infrared spectroscopy, FT Raman and Raman detector. An empty column is uniformly packed with the solid
8072 https://dx.doi.org/10.1021/acssuschemeng.9b06263
ACS Sustainable Chem. Eng. 2020, 8, 8059−8085
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Perspective

Figure 4. In situ tracking of lignin, cellulose, and xylan in corn stover cell walls by SRS before and after xylan digestion. (A) Comparison of bright-field
images of cell walls and SRS images of lignin, cellulose, and xylan in the same cell walls. (B) Comparison of the relative overall SRS signal change in the
images (before enzyme digestion = 100%) (Lig, lignin; Cel, cellulose; and Xyl, xylan; error bars are from five replicate experiments). Lignin and
cellulose are not affected by xylanases, and xylan is significantly reduced due to xylanases digestion. (C) Zoom-in bright-field images of cell wall and
SRS images of xylan in two areas in vascular bundle region (C1−4, before xylan digestion; C1′−4′, after xylan digestion) show significant xylan
distribution changes in the cell wall due to heterogeneous enzymatic digestion. Raman frequencies used for SRS imaging: lignin, 1600 cm−1; cellulose,
1100 cm−1; and xylan, 1471 cm−1. Scale bar = 20 μm. Reprinted from ref 220 with permission.

material to be analyzed (ideally powder, fiber, or film). Several
injections or pulses of probe molecule vapor are injected into the
column at a known concentration and carried via a fixed helium
gas flow rate. The elution time of the probes is dependent on the
physical adsorption and interactions with the surface of the solid
material. The property measured by IGC is the retention volume
VN, a measurement of how strongly probe molecules interact
with the solid material in the column. From a variety of probe
molecules and surface coverages, certain thermodynamic
properties can be attained (free energy, enthalpy, and entropy
of adsorption).20,21
Information gathered on biomass, such as the work of
cohesion, can be compared to the work of adhesion of a liquid. A
study involving the flowability of infant milk formula presents
evidence that a larger work of cohesion than the work of
adhesion contributes to poor rehydration or wettability.234
Indeed, there are other factors to consider in biomass, such as
initial moisture content, surface area, porosity, and hierarchal
structures (some structures are very hydrophobic) that
contribute to wettability. Surface energy (and perhaps atomic
force microscopy) measurements in conjunction with water
sorption (wettability) experiments can explore the impact that
8073
particle−particle interactions have on materials handling, i.e.,
ratholing, arching, and buckling. Recently, surface energy data
on corn stover have revealed differences between anatomical
fractions and even larger changes (specific component) in
thermally treated material.235
Surface Texture. Surface texture is an important physical
attribute of biomass that affects transport, storage, conveyance,
and physicochemical conversion.33 In particular, it can affect the
energy consumption required during biomass grinding.236 The
surface is the object boundary where particle interactions take
place, and the texture contributes to the surface behavior and
performance.237 The total profile of the surface texture is
composed of roughness, waviness, and error of form.237 Of
these, surface roughness is particularly important because its
contribution to friction and other mechanical interactions
between particles has an impact on flowability.33,238 Higher
surface roughness may also lead to a higher bulk density because
the higher friction between surfaces may limit the particles
ability to move into pores and compact.238 A positive aspect of
rougher surfaces in the context of biomass is that rougher
surfaces have a higher self-cleaning ability.239 This is due to the
higher hydrophobicity of rough surfaces compared to smoother
https://dx.doi.org/10.1021/acssuschemeng.9b06263
ACS Sustainable Chem. Eng. 2020, 8, 8059−8085
ACS Sustainable Chemistry & Engineering
Figure 5. In situ 3D SRS imaging to track xylan distribution in corn
stover cell walls before and after xylan digestion. (A−D) Before
digestion. (A′−D′) Same cell wall regions in A−D after xylanases
digestion for comparison. Xylan Raman frequency at 1471 cm−1 was
chosen for SRS imaging. (A, B, A′, B′) Cell corner. (C, D, C′, D′) Cell
wall between two cell corners. Reprinted from ref 210 with permission.
surfaces240,241 which enables water to roll off and wash off
contaminants, often called the lotus effect.239
Surface texture can be measured directly from images take by
laser profilometer,29 stereomicroscope,30,31 photographic scan-
ner,32 or scanning electron microscope. The image analysis can
be performed using ImageJ242 and the plugin SurfCharJ 1q.29,243
This plugin provides information on the surface roughness
based on grayscale values of the image or height map.29 Surface
texture may also be quantified using the gray-level co-occurrence
matrix (GLCM) method using SEM images.32,244,245
In addition, surface functional groups and properties in micro-
and nanoscale are needed for the mechanistic understanding of
the biomass conversion process. The pore structure and
wettability variation in physicochemical treatments is another
exciting area to help understand biomass properties. Efforts
should be made to investigate the variability of biomass physical
and mechanical properties and their effects on the handling
operations and conversion performance. The design of
processes and reactors can be optimized based on a
comprehensive understanding of feedstock properties and
their correlations.
■
CONCLUSIONS
In this perspective, we described physical, chemical, mechanical,
and other properties of biomass. Advanced analytical methods
that measure these properties were described along with the
8074
pubs.acs.org/journal/ascecg Perspective
limitations of their application. Also, the effects of these biomass
properties on feedstock handling, grinding, feeding, process
treatment, and conversion efficiency were discussed. Phys-
icochemical properties significantly interact among themselves.
These interactions are complicated and vary by type of biomass
and processing methods. The physical properties of bulk
biomass have a great impact on biomass processing and
conversion. Micromorphological changes from before and
after the treatments can be used to predict process yields.
Chemical analyses can indicate the onset of drastic physical
property changes after harvest, storage, preprocessing, and
conversion of biomass feedstock and provide guidelines for
evaluating and possibly improving feedstock quality. In
summary, it is challenging to interpret or predict the potential
behavior or conversion performance of feedstocks based on any
single characterization measurement. For a biorefinery to be
equipped to address feedstock variability as it arrives at a
biorefinery gate, it is essential to study multiple attributes and
obtain a comprehensive understanding of their potential
implications on feedstock conversion performance and opera-
tional reliability.
■ AUTHOR INFORMATION
Corresponding Authors
Allison E. Ray − Energy & Environment Science & Technology,
Idaho National Laboratory, Idaho Falls, Idaho 83415, United
States; orcid.org/0000-0002-5191-1029; Phone: (208)
526-4554; Email: allison.ray@inl.gov
Deepti Tanjore − Advanced Biofuels and Bioproducts Process
Development Unit and Biological Systems and Engineering
Division, Lawrence Berkeley National Laboratory, Emeryville,
California 94608, United States; orcid.org/0000-0001-
6507-4359; Phone: 510-486-6053; Email: DTanjore@lbl.gov
Authors
Jipeng Yan − Advanced Biofuels and Bioproducts Process
Development Unit and Biological Systems and Engineering
Division, Lawrence Berkeley National Laboratory, Emeryville,
California 94608, United States
Oluwafemi Oyedeji − Environmental Sciences Division, Oak
Ridge National Laboratory, Oak Ridge, Tennessee 37830, United
States; orcid.org/0000-0002-8684-425X
Juan H. Leal − Materials Physics & Applications, Los Alamos
National Laboratory, Los Alamos, New Mexico 87544, United
States
Bryon S. Donohoe − Biosciences Center, National Renewable
Energy Laboratory, Golden, Colorado 80403, United States;
orcid.org/0000-0002-2272-5059
Troy A. Semelsberger − Materials Physics & Applications, Los
Alamos National Laboratory, Los Alamos, New Mexico 87544,
United States; orcid.org/0000-0001-8827-7298
Chenlin Li − Energy & Environment Science & Technology, Idaho
National Laboratory, Idaho Falls, Idaho 83415, United States;
orcid.org/0000-0002-0793-0505
Amber N. Hoover − Energy & Environment Science &
Technology, Idaho National Laboratory, Idaho Falls, Idaho
83415, United States; orcid.org/0000-0001-8584-3995
Erin Webb − Environmental Sciences Division, Oak Ridge
National Laboratory, Oak Ridge, Tennessee 37830, United
States; orcid.org/0000-0002-1501-8647
Elizabeth A. Bose − Biosciences Center, National Renewable
Energy Laboratory, Golden, Colorado 80403, United States
https://dx.doi.org/10.1021/acssuschemeng.9b06263
ACS Sustainable Chem. Eng. 2020, 8, 8059−8085
ACS Sustainable Chemistry & Engineering
Yining Zeng − Biosciences Center, National Renewable Energy
Laboratory, Golden, Colorado 80403, United States
C. Luke Williams − Energy & Environment Science &
Technology, Idaho National Laboratory, Idaho Falls, Idaho
83415, United States; orcid.org/0000-0002-1935-0110
Kastli D. Schaller − Energy & Environment Science &
Technology, Idaho National Laboratory, Idaho Falls, Idaho
83415, United States
Ning Sun − Advanced Biofuels and Bioproducts Process
Development Unit and Biological Systems and Engineering
Division, Lawrence Berkeley National Laboratory, Emeryville,
California 94608, United States; orcid.org/0000-0002-
9689-9430
Complete contact information is available at:
https://pubs.acs.org/10.1021/acssuschemeng.9b06263
Notes
The authors declare no competing financial interest.
Biographies
Dr. Jipeng Yan (jipengyan@lbl.gov) currently works as a Senior Process
Engineer at the Advanced Biofuels and Bioproducts Process Develop-
ment Unit (ABPDU), Lawrence Berkeley National Laboratory. Dr. Yan
has extensive research experience in the development of protein
purification, lignin fractionation, biomass pretreatment, and bio-
products recovery. At ABPDU, Dr. Yan focuses on developing
technologies as well as managing projects related to biomass
deconstruction (i.e., pretreatment and hydrolysis) and downstream
conversion and upgrading activities such as fermentation and chemical
processing. Dr. Yan completed his Ph.D. in paper and bioprocess
engineering at SUNY College of Environmental Sciences and Forestry.
The focus of his thesis was the production of ethanol using woody
biomass. Among his many accomplishments, he built kinetic models for
monosaccharides, oligosaccharides, furfural, hydroxymethylfurfural,
formic acid, and acetyl groups.
Dr. Oluwafemi Oyedeji (oyedejia@ornl.gov) is an R&D Assistant Staff
member at the Environmental Sciences Division of Oak Ridge National
Laboratory. He completed his Ph.D. in biosystems engineering at the
University of Tennessee in 2019 and his M.S. in biosystems engineering
at Auburn University 2015. He also earned an M.S. in chemical
engineering from the University of Tennessee in 2018. His research
focuses on exploring multiscale modeling approaches for optimizing
8075
pubs.acs.org/journal/ascecg Perspective
biomass logistics supply and conversion systems. He has authored and
coauthored several publications on biomass preparation and conversion
processes.
Dr. Juan H. Leal (jhleal@lanl.gov) is a Postdoctoral Researcher in
materials synthesis and integrated devices (MPA-11) at Los Alamos
National Laboratory. He received his B.S. and M.S. degrees in biology
and chemistry from the University of Texas Rio Grande Valley and
Ph.D. in material science and engineering from the University of Texas
at El Paso. Dr. Leal focuses on surface energy characterization of
variable lignocellulosic material with relation to adhesive, cohesive, and
wettability effects. Currently, he serves on the Feedstock Variability
Task as part of the Feedstock Conversion Interface Consortium
(FCIC) that is funded through the U.S. Department of Energy (DOE)
Bioenergy Technologies Office (BETO).
Dr. Bryon S. Donohoe (bryon.donohoe@nrel.gov) is a Senior Scientist
in the Biosciences Center at the National Renewable Energy
Laboratory (NREL). He received his Ph.D. from the University of
Colorado and trained in the Boulder Laboratory for 3D Electron
Microscopy of Cells. His current research focuses on determining
mechanisms of thermal, chemical, and biological deconstruction of
plant and algal biomass and other complex polymer materials. He is an
expert in the use of imaging and structural cell biology approaches to
gain insight into cell wall architecture, enzyme/substrate interactions,
and effectiveness of bioconversion technologies.
Dr. Troy A. Semelsberger (troy@lanl.gov) is a Staff Scientist in
Materials Synthesis and Integrated Devices (MPA-11) at Los Alamos
National Laboratory. He received a B.A. in chemistry from the College
of Wooster and his B.S., M.S., and Ph.D. in chemical engineering from
Case Western Reserve University. Currently, he is the LANL PI and the
Co-Task Lead for the Materials Handling Task in the Feedstock
Conversion Interface Consortium (FCIC) funded through the U.S.
https://dx.doi.org/10.1021/acssuschemeng.9b06263
ACS Sustainable Chem. Eng. 2020, 8, 8059−8085
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Perspective

Department of Energy (DOE) Bioenergy Technologies Office

(BETO).

Dr. Erin Webb (webbeg@ornl.gov), Ph.D., P.E., is a Senior R&D Staff

Member in the Environmental Sciences Division at Oak Ridge National
Dr. Chenlin Li (Chenlin.li@inl.gov) is a Distinguished Staff Engineer in Laboratory. She received a B.S. in agricultural engineering from the
the Energy and Environment Science and Technology Directorate at University of Tennessee, M.S. in biosystems engineering from the
Idaho National Laboratory (INL). She leads INL’s activities within the University of Kentucky, and Ph.D. in agricultural and biological
Feedstock-Conversion Interface R&D, primarily sponsored by the engineering from the University of Florida. Dr. Webb now leads
Bioenergy Technologies Office of the U.S. Department of Energy. She multiple projects sponsored by the Department of Energy focused on
is also the Deputy Laboratory Relationship Manager for INL’s simulation and analysis of supply chains to deliver biomass as a
Bioenergy Program. Prior to joining Idaho National Laboratory, she feedstock for production of fuels, products, and power.
led and performed innovative research and development on
lignocellulosic biofuels and waste to bioenergy at Lawrence Berkeley
National Laboratory, Sandia National Laboratories, and multiple
universities in the United States and China. Dr. Li received her
bachelor’s and master’s degrees in chemical engineering from
Zhengzhou University and Ph.D. in environmental engineering from
the University of Hong Kong, China. She has been a U.S. national team
member of the International Energy Agency Bioenergy Task 40
Deployment of Biobased Value Chains since 2018.
Ms. Elizabeth A. Bose (email: eliza97@vt.edu) is a fifth-year
undergraduate student at Virginia Tech, having completed a B.S. in
clinical neuroscience and continuing to finish a B.S. in biochemistry. A
four-year letter winner on the Virginia Tech Varsity women’s golf team,
Elizabeth has also completed undergraduate research with the Virginia
Tech Department of Biochemistry with Dr. Robert White and with the
joint Vinauger−Lahondere laboratory. She was awarded a SULI
internship from the U.S. Department of Energy to work at NREL with
Dr. Bryon Donohoe where she studied the surface properties of plant
Amber N. Hoover (Amber.hoover@inl.gov) is a Research Scientist in biomass through optical and electron microscopy, statistical image
the Biomass Characterization group at Idaho National Laboratory. She analysis.
has been involved in a variety of projects for the U.S. Department of
Energy’s Bioenergy Technologies Office, including research related to
the development of a conversion-based grading system for biomass
resources, the effects of drought on plant chemistry and subsequent
performance in biochemical conversion processes, and biomass
densification. Her current work focuses on how environmental
variables, genetics, production factors, anatomical fractions, and storage
alter biomass physical and chemical properties that impact quality for
downstream processes. Hoover also supports biofuels research at Idaho
National Laboratory by serving as a leader for the Biomass Feedstock Dr. Yining Zeng (yining.zeng@nrel.gov) received his B.S. and M.S. in
National User Facility Biomass Characterization Lab and as an chemistry from Peking University in China and his Ph.D. from the
administrator for the Bioenergy Feedstock Library, a database of University of Texas at Austin. Yining is a Staff Scientist at the National
biomass characterization data linked to a physical repository of biomass Renewable Energy Laboratory and is working on developing
samples. She holds a master’s degree in biology from Idaho State spectroscopic tools to probe material properties and biological
University and a bachelor’s degree in biology from Penn State processes. Particularly, his research interests include the development
University. and use of single-molecule spectroscopy and label-free imaging.

8076 https://dx.doi.org/10.1021/acssuschemeng.9b06263
ACS Sustainable Chem. Eng. 2020, 8, 8059−8085
ACS Sustainable Chemistry & Engineering
Kastli Schaller (kastli.schaller@inl.gov), M.S., is a Research Scientist at
the Idaho National Laboratory in the Chemical and Radiation
Measurement Department. She has supported multiple programs
with analysis and characterization of biomass materials for the last 5
years. She has a B.S. degree from the University of Nevada, Reno, and a
M.S. from Idaho State University.
Dr. Ning Sun (nsun@lbl.gov) is a Research Scientist at Lawrence
Berkeley National Laboratory. Her research is primarily focused on
combined biological and chemical pathways to convert lignocellulosic
biomass to biofuels and biobased products. She has integrated catalysis,
characterization, and techno-economic analysis into her team’s research
in order to develop an efficient biomass conversion process that is both
technically sound and economically feasible. Her research also includes
characterization and evaluation of the solid and liquid streams from the
biomass conversion process and the development of integrated
processes for biomass upgrading.
Dr. C. Luke Williams (luke.williams@inl.gov) joined the Idaho
National Laboratory as a Research Scientist in September 2014 and
has focused his research on lignocellulosic biomass harvest, chemical
and physical characterization, material handling, and thermochemical
conversion screening. Prior to joining Idaho National Laboratory, he
received his Ph.D. in chemical engineering from the University of
Massachusetts Amherst, where his research focused on catalytic
reaction engineering for the production of renewable aromatic
chemicals from biomass-derived sugars.
8077
pubs.acs.org/journal/ascecg Perspective
Dr. Allison E. Ray (allison.ray@inl.gov) is the Research Excellence Lead
for Science and Technology and a Senior Research Scientist at Idaho
National Laboratory. She received her B.S. and M.S. degrees in
agricultural and biological engineering from Purdue University and
Ph.D. in environmental microbiology from Idaho State University.
Currently, she leads the Feedstock Variability Task as part of the
Feedstock Conversion Interface Consortium (FCIC) that is funded
through the U.S. Department of Energy (DOE) Bioenergy
Technologies Office (BETO).
Deepti Tanjore (dtanjore@lbl.gov) is the Director of Advanced
Biofuels and Bioproducts Process Development Unit (ABPDU) at
Lawrence Berkeley National Laboratory. Deepti has significant
experience in a broad spectrum of biochemical and chemical unit
operations applicable to the conversion of lignocellulosic biomass to
bioproducts. Deepti’s research at ABPDU focuses on processes that
integrate chemical and biological pathways in the production of new
generation compounds and developing real-time and/or online
analytical tools for adequate regulation during the scale-up of these
processes.
■ ACKNOWLEDGMENTS
The authors acknowledge the funding support from the
Bioenergy Technologies Office within the DOE Energy
Efficiency and Renewable Energy Office through the Feedstock
Conversion Interface Consortium. This work was authored in
part by Alliance for Sustainable Energy, LLC, the manager and
operator of the National Renewable Energy Laboratory for the
U.S. Department of Energy (DOE) under Contract No. DE-
AC36-08GO28308. Idaho National Laboratory coauthors
acknowledge the funding support from DOE under DOE
Idaho Operations Office Contract DE-AC07-05ID14517. The
views expressed in the article do not necessarily represent the
views of the DOE or the U.S. Government. The U.S.
Government retains and the publisher, by accepting the article
for publication, acknowledges that the U.S. Government retains
a nonexclusive, paid-up, irrevocable, worldwide license to
publish or reproduce the published form of this work or allow
others to do so, for U.S. Government purposes. The authors also
thank Emily Scott for preparing some of the graphics in this
perspective.
https://dx.doi.org/10.1021/acssuschemeng.9b06263
ACS Sustainable Chem. Eng. 2020, 8, 8059−8085
ACS Sustainable Chemistry & Engineering
■
REFERENCES
(1) U.S. Energy Information Administration. Biomass Explained.
BiomassRenewable Energy from Plants and Animals. https://www.eia.
gov/energyexplained/index.php?page=biomass_home (accessed Dec
1, 2019).
(2) U.S. Department of Energy. 2016 Billion-Ton Report: Advancing
Domestic Resources for a Thriving Bioeconomy, Volume 1: Economic
Availablity of Feedstocks. Langholtz, M. H.; Stokes, B. J.; Eaton, L. M.,
Eds.; Oak Ridge National Laboratory: Oak Ridge, TN, 2016,
DOI: 10.2172/1271651.
(3) Lamers, P.; Tan, E. C. D.; Searcy, E. M.; Scarlata, C. J.; Cafferty, K.
G.; Jacobson, J. J. Strategic supply system design − a holistic evaluation
of operational and production cost for a biorefinery supply chain.
Biofuels, Bioprod. Biorefin. 2015, 9 (6), 648−660.
(4) Narani, A.; Coffman, P.; Gardner, J.; Li, C.; Ray, A. E.; Hartley, D.
S.; Stettler, A.; Konda, N. V. S. N. M.; Simmons, B.; Pray, T. R.;
Tanjore, D. Predictive modeling to de-risk bio-based manufacturing by
adapting to variability in lignocellulosic biomass supply. Bioresour.
Technol. 2017, 243, 676−685.
(5) Williams, C. L.; Westover, T. L.; Emerson, R. M.; Tumuluru, J. S.;
Li, C. Sources of Biomass Feedstock Variability and the Potential
Impact on Biofuels Production. BioEnergy Res. 2016, 9 (1), 1−14.
(6) Cai, J.; He, Y.; Yu, X.; Banks, S. W.; Yang, Y.; Zhang, X.; Yu, Y.; Liu,
R.; Bridgwater, A. V. Review of physicochemical properties and
analytical characterization of lignocellulosic biomass. Renewable
Sustainable Energy Rev. 2017, 76, 309−322.
(7) Naik, S.; Goud, V. V.; Rout, P. K.; Jacobson, K.; Dalai, A. K.
Characterization of Canadian biomass for alternative renewable biofuel.
Renewable Energy 2010, 35 (8), 1624−1631.
(8) Sanderson, M. A.; Agblevor, F.; Collins, M.; Johnson, D. K.
Compositional analysis of biomass feedstocks by near infrared
reflectance spectroscopy. Biomass Bioenergy 1996, 11 (5), 365−370.
(9) Mohan, D.; Pittman, C. U.; Steele, P. H. Pyrolysis of Wood/
Biomass for Bio-oil: A Critical Review. Energy Fuels 2006, 20 (3), 848−
889.
(10) Kenney, K.; Smith, W.; Gresham, G.; Westover, T. Under-
standing Biomass Feedstock Variability. Biofuels 2013, 4, 111−127.
(11) Li, C.; Tanjore, D.; He, W.; Wong, J.; Gardner, J. L; Sale, K. L;
Simmons, B. A; Singh, S. Scale-up and evaluation of high solid ionic
liquid pretreatment and enzymatic hydrolysis of switchgrass. Biotechnol.
Biofuels 2013, 6, 154−166.
(12) Sundstrom, E.; Yaegashi, J.; Yan, J.; Masson, F.; Papa, G.;
Rodriguez, A.; Mirsiaghi, M.; Liang, L.; He, Q.; Tanjore, D.; Pray, T. R.;
Singh, S.; Simmons, B.; Sun, N.; Magnuson, J.; Gladden, J.
Demonstrating a separation-free process coupling ionic liquid pretreat-
ment, saccharification, and fermentation with Rhodosporidium
toruloides to produce advanced biofuels. Green Chem. 2018, 20 (12),
2870−2879.
(13) Yan, J.; Liang, L.; He, Q.; Li, C.; Xu, F.; Sun, J.; Goh, E.-B.;
Konda, N. V. S. N. M.; Beller, H. R.; Simmons, B. A.; Pray, T. R.;
Thompson, V. S.; Singh, S.; Sun, N. Methyl Ketones from Municipal
Solid Waste Blends by One-Pot Ionic-Liquid Pretreatment, Saccha-
rification, and Fermentation. ChemSusChem 2019, 12 (18), 4313−
4322.
(14) Edwards, H. G. M.; Farwell, D. W.; Webster, D. FT Raman
microscopy of untreated natural plant fibres. Spectrochim. Acta, Part A
1997, 53 (13), 2383−2392.
(15) Raveendran, K.; Ganesh, A.; Khilar, K. C. Pyrolysis character-
istics of biomass and biomass components. Fuel 1996, 75 (8), 987−998.
(16) O’SULLIVAN, A. C. Cellulose: the structure slowly unravels.
Cellulose 1997, 4 (3), 173−207.
(17) White, J. E.; Catallo, W. J.; Legendre, B. L. Biomass pyrolysis
kinetics: A comparative critical review with relevant agricultural residue
case studies. J. Anal. Appl. Pyrolysis 2011, 91 (1), 1−33.
(18) Dirion, J.-L.; Reverte, C.; Cabassud, M. Kinetic parameter
estimation from TGA: Optimal design of TGA experiments. Chem. Eng.
Res. Des. 2008, 86 (6), 618−625.
8078
pubs.acs.org/journal/ascecg Perspective
(19) Conesa, J. A.; Urueña, A.; Díez, D. Corn stover thermal
decomposition in pyrolytic and oxidant atmosphere. J. Anal. Appl.
Pyrolysis 2014, 106, 132−137.
(20) Smidsrød, O.; Guillet, J. E. Study of Polymer-Solute Interactions
by Gas Chromatography. Macromolecules 1969, 2 (3), 272−277.
(21) Hegedus, C. R.; Kamel, I. L. Review of inverse gas
chromatography theory used in the thermodynamic analysis of pigment
and polymer surfaces. J. Coat. Technol. Res. 1993, 65 (820), na.
(22) Xu, F.; Yu, J.; Tesso, T.; Dowell, F.; Wang, D. Qualitative and
quantitative analysis of lignocellulosic biomass using infrared
techniques: A mini-review. Appl. Energy 2013, 104, 801−809.
(23) Hames, B.; Thomas, S.; Sluiter, A.; Roth, C.; Templeton, D.
Rapid biomass analysis: new tools for compositional analysis of corn
stover feedstocks and process intermediates from ethanol production.
Appl. Biochem. Biotechnol. 2003, 105−108, 5−16.
(24) Li, C.; Sun, L.; Simmons, B. A.; Singh, S. Comparing the
Recalcitrance of Eucalyptus, Pine, and Switchgrass Using Ionic Liquid
and Dilute Acid Pretreatments. BioEnergy Res. 2013, 6 (1), 14−23.
(25) Yuan, W.; Gong, Z.; Wang, G.; Zhou, W.; Liu, Y.; Wang, X.;
Zhao, M. Alkaline organosolv pretreatment of corn stover for enhancing
the enzymatic digestibility. Bioresour. Technol. 2018, 265, 464−470.
(26) Jähn, A.; Schrö der, M. W.; Fü ting, M.; Schenzel, K.;
Diepenbrock, W. Characterization of alkali treated flax fibres by
means of FT Raman spectroscopy and environmental scanning electron
microscopy. Spectrochim. Acta, Part A 2002, 58 (10), 2271−2279.
(27) Kiemle, D. J.; Stipanovic, A. J.; Mayo, K. E. Proton NMR
Methods in the Compositional Characterization of Polysaccharides. In
Hemicelluloses: Science and Technology; Gatenholm, P., Tenkanen, M.,
Eds.; ASC Symposium Series 864; American Chemical Society:
Washington, DC, 2003; pp 122−139.
(28) Capanema, E. A.; Balakshin, M. Y.; Kadla, J. F. A Comprehensive
Approach for Quantitative Lignin Characterization by NMR Spectros-
copy. J. Agric. Food Chem. 2004, 52 (7), 1850−1860.
(29) CHINGA, G.; JOHNSEN, P. O.; DOUGHERTY, R.; BERLI, E.
L.; WALTER, J. Quantification of the 3D microstructure of SC surfaces.
J. Microsc. 2007, 227 (3), 254−265.
(30) Mitra, A.; Li, Y.-F.; Klämpfl, T. G.; Shimizu, T.; Jeon, J.; Morfill,
G. E.; Zimmermann, J. L. Inactivation of Surface-Borne Micro-
organisms and Increased Germination of Seed Specimen by Cold
Atmospheric Plasma. Food Bioprocess Technol. 2014, 7 (3), 645−653.
(31) Piselli, A.; Basso, M.; Simonato, M.; Furlanetto, R.; Cigada, A.;
De Nardo, L.; Del Curto, B. Effect of wear from cleaning operations on
sintered ceramic surfaces: Correlation of surface properties data with
touch perception and digital image processing. Wear 2017, 390, 355.
(32) Aguirre, A.; Karwe, M. V.; Borneo, R. Effect of high pressure
processing on sugar-snap cookie dough preservation and cookie quality.
J. Food Process. Preserv. 2018, 42 (1), No. e13407.
(33) Dai, J.; Cui, H.; Grace, J. R. Biomass feeding for thermochemical
reactors. Prog. Energy Combust. Sci. 2012, 38 (5), 716−736.
(34) Foston, M.; Ragauskas, A. J. Biomass Characterization: Recent
Progress in Understanding Biomass Recalcitrance. Ind. Biotechnol.
2012, 8 (4), 191−208.
(35) Ray, A. E.; Williams, C. L.; Hoover, A. N.; Li, C.; Sale, K. L.;
Emerson, R. M.; Klinger, J.; Oksen, E.; Narani, A.; Yan, J.; Beavers, C.
M.; Tanjore, D.; Yunes, M.; Bose, E.; Leal, J. H.; Bowen, J. L.; Wolfrum,
E. J.; Resch, M. G.; Semelsberger, T. A.; Donohoe, B. S. Multiscale
Characterization of Lignocellulosic Biomass Variability and Its
Implications to Preprocessing and Conversion: a Case Study for
Corn Stover. ACS Sustainable Chem. Eng. 2020, 8 (8), 3218−3230.
(36) Tan, E. C. D.; Talmadge, M.; Dutta, A.; Hensley, J.; Schaidle, J.;
Biddy, M.; Humbird, D.; Snowden-Swan, L. J.; Ross, J.; Sexton, D.; et al.
Process Design and Economics for the Conversion of Lignocellulosic Biomass
to Hydrocarbons via Indirect Liquefaction; NREL/TP-5100-62402,
PNNL-23822; National Renewable Energy Laboratory and Pacific
Northwest National Laboratory, 2015, DOI: 10.2172/1483234.
(37) Oginni, O.; Fasina, O. Theoretical Estimation of Silo Design
Parameters for Fractionated Loblolly Pine Grinds − Moisture Content
and Particle Size Effects. Ind. Crops Prod. 2018, 123 (1), 379−385.
https://dx.doi.org/10.1021/acssuschemeng.9b06263
ACS Sustainable Chem. Eng. 2020, 8, 8059−8085
ACS Sustainable Chemistry & Engineering
(38) Ileleji, K. E.; Zhou, B. The Angle of Repose of Bulk Corn Stover
Particles. Powder Technol. 2008, 187 (2), 110−118.
(39) Oyedeji, O.; Fasina, O. Impact of Drying-Grinding Sequence on
Loblolly Pine Chips Preprocessing Effectiveness. Ind. Crops Prod. 2017,
96, 8.
(40) Miao, Z.; Grift, T. E.; Hansen, A. C.; Ting, K. C. Energy
requirement for comminution of biomass in relation to particle physical
properties. Ind. Crops Prod. 2011, 33 (2), 504−513.
(41) Paulrud, S.; Mattsson, J. E.; Nilsson, C. Particle and Handling
Characteristics of Wood Fuel Powder: Effects of Different Mills. Fuel
Process. Technol. 2002, 76 (1), 23−39.
(42) Hehar, G.; Fasina, O.; Adhikari, S.; Fulton, J. Ignition and
Volatilization Behavior of Dust from Loblolly Pine Wood. Fuel Process.
Technol. 2014, 127 (1), 117−123.
(43) Wang, Y.; Yan, L. CFD Studies on Biomass Thermochemical
Conversion. Int. J. Mol. Sci. 2008, 9 (6), 1108−1130.
(44) Probst, K. V; Ambrose, R. P. K.; Pinto, R. L.; Bali, R.;
Krishnakumar, P.; Ileleji, K. E. The Effect of Moisture Content on the
Grinding Performance of Corn and Corncobs by Hammermilling.
Trans. ASABE 2013, 56 (3), 1025−1033.
(45) Oyedeji, O.; Young, A.; Fasina, O. Bending Properties of Loblolly
Pine. Ind. Crops Prod. 2017, 109, 905.
(46) Phanphanich, M.; Mani, S. Impact of torrefaction on the
grindability and fuel characteristics of forest biomass. Bioresour. Technol.
2011, 102 (2), 1246−1253.
(47) McKendry, P. Energy production from biomass (part 1):
overview of biomass. Bioresour. Technol. 2002, 83 (1), 37−46.
(48) Wang, L. Sustainable Bioenergy Production; Taylor & Francis,
2014.
(49) Lawrence, M.; Jiang, Y. Porosity, Pore Size Distribution, Micro-
structure; Springer Netherlands, 2017; Chapter 2, DOI: 10.1007/978-
94-024-1031-0_2.
(50) Miao, Z.; Grift, T. E.; Hansen, A. C.; Ting, K. C. Flow
performance of ground biomass in a commercial auger. Powder Technol.
2014, 267, 354−361.
(51) Yu, A. B.; Standish, N.; Lu, L. Coal agglomeration and its effect
on bulk density. Powder Technol. 1995, 82 (2), 177−189.
(52) Adapa, P.; Tabil, L.; Schoenau, G. Grinding performance and
physical properties of non-treated and steam exploded barley, canola,
oat and wheat straw. Biomass Bioenergy 2011, 35 (1), 549−561.
(53) Goncalves, B.; Till, D.; Fasina, O.; Tamang, B.; Gallagher, T.
Influence of Bark on the Physical and Thermal Decomposition
Properties of Short-Rotation Eucalyptus. BioEnergy Res. 2015, 8 (3),
1414−1423.
(54) Theerarattananoon, K.; Xu, F.; Wilson, J.; Ballard, R.; McKinney,
L.; Staggenborg, S.; Vadlani, P.; Pei, Z. J.; Wang, D. Physical properties
of pellets made from sorghum stalk, corn stover, wheat straw, and big
bluestem. Ind. Crops Prod. 2011, 33 (2), 325−332.
(55) Tumuluru, J. S. Effect of pellet die diameter on density and
durability of pellets made from high moisture woody and herbaceous
biomass. Carbon Resources Conversion 2018, 1 (1), 44−54.
(56) Colley, Z.; Fasina, O. O.; Bransby, D.; Lee, Y. Y. Moisture Effect on
the Physical Characteristics of Switchgrass Pellets; AGRIS, 2006; pp
1845−1851.
(57) rBanks, S. Ash Control Methods to Limit Biomass Inorganic Content
and Its Effect on Fast Pyrolysis Bio-Oil Stability. Ph.D. Thesis, Aston
University, Birmingham, U.K., 2014.
(58) Oginni, O. J. Contribution of Particle Size and Moisture Content
to Flowability of Fractionated Ground Loblolly Pine. Ph.D. Thesis,
Auburn University, Auburn, Alabama, USA, 2014.
(59) Lam, P. S.; Sokhansanj, S.; Bi, X.; Lim, C. J.; Naimi, L. J.; Hoque,
M.; Mani, S.; Womac, A. R.; Narayan, S.; Ye, X. P. Bulk Density of Wet
and Dry Wheat Straw and Switchgrass Particles. Appl. Eng. Agric. 2008,
24 (3), 351−358.
(60) ASTM D1895-9: Standard Test Methods for Apparent Density,
Bulk Factor and Pourability of Plastic Materials; American Society for
Testing and Materials: West Conshohocken, PA, 2010, DOI: 10.1520/
D1895-96.
8079
pubs.acs.org/journal/ascecg Perspective
(61) ASTM E873-82: Standard Test Method for Bulk Density of
Densified Particulate Biomass Fuels; American Society for Testing and
Materials: West Conshohocken, PA, 2019, DOI: 10.1520/E0873-
82R19.
(62) ASABE S269.5: Densified Products for Bulk Handling
Definitions and Method. In ASABE Standards 2012; American Society
of Agricultural and Biological Engineers: St. Joseph, MI, 2012.
(63) Lam, P. S.; Sokhansanj, S. Engineering Properties of Biomass;
Springer: New York, 2014, DOI: 10.1007/978-1-4899-8014-4_2p 17-
35.
(64) Igathinathane, C.; Davis, J. D.; Purswell, J. L.; Columbus, E. P.
Application of 3D scanned imaging methodology for volume, surface
area, and envelope density evaluation of densified biomass. Bioresour.
Technol. 2010, 101 (11), 4220−4227.
(65) Oyedeji, O.; Gitman, P.; Qu, J.; Webb, E. Understanding the
Impact of Lignocellulosic Biomass Variability on the Size Reduction
Process: A Review. ACS Sustainable Chem. Eng. 2020, 8, 2327.
(66) Fasina, O. O. Measuring Grain and Legume Seed Density Using
Pycnometer and Envelope Density Analyzer; American Society of
Agricultural and Biological Engineers, 2010; pp 1223−1227.
(67) Igathinathane, C.; Tumuluru, J. S.; Sokhansanj, S.; Bi, X.; Lim, C.
J.; Melin, S.; Mohammad, E. Simple and inexpensive method of wood
pellets macro-porosity measurement. Bioresour. Technol. 2010, 101
(16), 6528−6537.
(68) Unified Facilities Criteria (UFC): Army Filtration of Liquids; UFC
3-280-04; U.S. Department of Defense, 2003.
(69) Rouquerol, J.; Rouquerol, F.; Llewellyn, P.; Maurin, G.
Adsorption by Powders and Porous Solids: Principles, Methodology and
Applications; Academic Press, 2013, DOI: 10.1016/B978-0-12-
598920-6.X5000-3.
(70) Lowell, S.; Shields, J. E.; Tomas, M.; Thommes, M. Character-
ization of Porous Solids and Powders: Surface Area, Pore Size and Density;
Springer: Dordrecht, 2012, DOI: 10.1007/978-1-4020-2303-3.
(71) Anovitz, L. M.; Cole, D. R. Characterization and Analysis of
Porosity and Pore Structures. Rev. Mineral. Geochem. 2015, 80 (1), 61−
164.
(72) Thommes, M.; Kaneko, K.; Neimark, A. V.; Olivier, J. P.;
Rodriguez-Reinoso, F.; Rouquerol, J.; Sing, K. S.W. Physisorption of
gases, with special reference to the evaluation of surface area and pore
size distribution (IUPAC Technical Report). Pure Appl. Chem. 2015, 87
(9−10), 1051.
(73) Herbaut, M.; Zoghlami, A.; Habrant, A.; Falourd, X.; Foucat, L.;
Chabbert, B.; Paës, G. Multimodal analysis of pretreated biomass
species highlights generic markers of lignocellulose recalcitrance.
Biotechnol. Biofuels 2018, 11 (1), 52.
(74) Xiao, P.-W.; Meng, Q.; Zhao, L.; Li, J.-J.; Wei, Z.; Han, B.-H.
Biomass-derived flexible porous carbon materials and their applications
in supercapacitor and gas adsorption. Mater. Des. 2017, 129, 164−172.
(75) Adani, F.; Papa, G.; Schievano, A.; Cardinale, G.; D’Imporzano,
G.; Tambone, F. Nanoscale Structure of the Cell Wall Protecting
Cellulose from Enzyme Attack. Environ. Sci. Technol. 2011, 45 (3),
1107−1113.
(76) Papadopoulos, A. N.; Hill, C. A. S.; Gkaraveli, A. Determination
of surface area and pore volume of holocellulose and chemically
modified wood flour using the nitrogen adsorption technique. Holz als
Roh- und Werkstoff 2003, 61 (6), 453−456.
(77) Brewer, C. E.; Chuang, V. J.; Masiello, C. A.; Gonnermann, H.;
Gao, X.; Dugan, B.; Driver, L. E.; Panzacchi, P.; Zygourakis, K.; Davies,
C. A. New approaches to measuring biochar density and porosity.
Biomass Bioenergy 2014, 66, 176−185.
(78) Noiriel, C. Resolving Time-dependent Evolution of Pore-Scale
Structure, Permeability and Reactivity using X-ray Microtomography.
Rev. Mineral. Geochem. 2015, 80 (1), 247.
(79) Rouquerol, J.; Avnir, D.; Fairbridge, C. W.; Everett, D. H.;
Haynes, J. M.; Pernicone, N.; Ramsay, J. D. F.; Sing, K. S. W.; Unger, K.
K. Recommendations for the characterization of porous solids. Pure
Appl. Chem. 2009, 66 (8), 1739.
https://dx.doi.org/10.1021/acssuschemeng.9b06263
ACS Sustainable Chem. Eng. 2020, 8, 8059−8085
ACS Sustainable Chemistry & Engineering
(80) Ishizawa, C. I.; Davis, M. F.; Schell, D. F.; Johnson, D. K. Porosity
and Its Effect on the Digestibility of Dilute Sulfuric Acid Pretreated
Corn Stover. J. Agric. Food Chem. 2007, 55 (7), 2575−2581.
(81) Meng, X.; Foston, M.; Leisen, J.; DeMartini, J.; Wyman, C. E.;
Ragauskas, A. J. Determination of porosity of lignocellulosic biomass
before and after pretreatment by using Simons’ stain and NMR
techniques. Bioresour. Technol. 2013, 144, 467−476.
(82) Guo, Q.; Chen, X.; Liu, H. Experimental research on shape and
size distribution of biomass particle. Fuel 2012, 94, 551−555.
(83) van Sjaak, L.; Jaap, K. The Handbook of Biomass Combustion and
Co-Firing; Earthscan: Sterling, VA, 2008.
(84) Yuan, Z.; Long, J.; Wang, T.; Shu, R.; Zhang, Q.; Ma, L. Process
intensification effect of ball milling on the hydrothermal pretreatment
for corn straw enzymolysis. Energy Convers. Manage. 2015, 101, 481−
488.
(85) Huang, Y.-F.; Kuan, W.-H.; Chang, C.-Y. Effects of particle size,
pretreatment, and catalysis on microwave pyrolysis of corn stover.
Energy 2018, 143, 696−703.
(86) Jiang, J.; Wang, J.; Zhang, X.; Wolcott, M. Evaluation of physical
structural features on influencing enzymatic hydrolysis efficiency of
micronized wood. RSC Adv. 2016, 6 (105), 103026−103034.
(87) Li, C.; Aston, J. E.; Lacey, J. A.; Thompson, V. S.; Thompson, D.
N. Impact of feedstock quality and variation on biochemical and
thermochemical conversion. Renewable Sustainable Energy Rev. 2016,
65, 525.
(88) Modenbach, A. A.; Nokes, S. E. Enzymatic hydrolysis of biomass
at high-solids loadings − A review. Biomass Bioenergy 2013, 56, 526−
544.
(89) Couper, J. R.; Penney, W. R.; Fair, J. R.; Walas, S. M.
Disintegration, Agglomeration, and Size Separation of Particulate
Solids. In Chemical Process Equipment: Selection and Design, Second ed.;
Elsevier, 2010; pp 361−397, DOI: 10.1016/B978-0-12-396959-
0.00012-4.
(90) Fowler, R. T.; Lim, S. C. The influence of various factors upon the
effectiveness of separation of a finely divided solid by a vibrating screen.
Chem. Eng. Sci. 1959, 10 (3), 163−170.
(91) Gu, Y. M.; Kim, H.; Sang, B.-I.; Lee, J. H. Effects of water content
on ball milling pretreatment and the enzymatic digestibility of corn
stover. Water-Energy Nexus 2018, 1 (1), 61−65.
(92) Cardona, J.; Ferreira, C.; McGinty, J.; Hamilton, A.; Agimelen, O.
S.; Cleary, A.; Atkinson, R.; Michie, C.; Marshall, S.; Chen, Y.-C.;
Sefcik, J.; Andonovic, I.; Tachtatzis, C. Image analysis framework with
focus evaluation for in situ characterisation of particle size and shape
attributes. Chem. Eng. Sci. 2018, 191, 208−231.
(93) Kempkes, M.; Vetter, T.; Mazzotti, M. Measurement of 3D
particle size distributions by stereoscopic imaging. Chem. Eng. Sci. 2010,
65 (4), 1362−1373.
(94) Zhang, R.; Ma, C. Y.; Liu, J. J.; Zhang, Y.; Liu, Y. J.; Wang, X. Z.
Stereo imaging camera model for 3D shape reconstruction of complex
crystals and estimation of facet growth kinetics. Chem. Eng. Sci. 2017,
160, 171−182.
(95) Cutshall, J.; Greene, D.; Baker, S.; Mitchell, D. Transpirational
Drying Effects on Energy and Ash Content from Whole-Tree Chipping
Operations in a Southern Pine Plantation. In Proceedings of the 34th
Council on Forest Engineering Annual Meeting, Quebec City, Quebec,
Canada, 2011; pp 1−9, DOI: 10.5849/sjaf.11-046pp.
(96) Kemmerer, B.; Liu, J. Effect of harvesting time and moisture
content on energy consumption of compressing switchgrass. Am. J.
Plant Sci. 2014, 05 (21), 3241.
(97) Karunanithy, C.; Muthukumarappan, K.; Donepudi, A. Moisture
Sorption Characteristics of Corn Stover and Big Bluestem. J. Renewable
Energy 2013, 2013, 1.
(98) Abdoulmoumine, N.; Kulkarni, A.; Adhikari, S. Effects of
Temperature and Equivalence Ratio on Pine Syngas Primary Gases and
Contaminants in a Bench-Scale Fluidized Bed Gasifier. Ind. Eng. Chem.
Res. 2014, 53 (14), 5767−5777.
(99) Jeoh, T.; Karuna, N.; Weiss, N. D.; Thygesen, L. G. Two-
Dimensional 1H-Nuclear Magnetic Resonance Relaxometry for
8080
pubs.acs.org/journal/ascecg Perspective
Understanding Biomass Recalcitrance. ACS Sustainable Chem. Eng.
2017, 5 (10), 8785−8795.
(100) Fisher, K. A new method for the analytical determination of the
water content of liquids and solids. Angew. Chem. 1935, na.
(101) ASAE Standard S358.2: Moisture Measurement - Forages;
ASABE: St. Joseph, MI, 2012, DOI: 10.13031/2013.41661.
(102) Kudra, T.; Raghavan, G. S. V. Post Harvest Technology of
Cereals Pulses and Oilseeds. Drying Technol. 1991, 9 (2), 527−528.
(103) Rowell, R. The Chemistry of Solid Wood; Advances in Chemistry
207; American Chemical Society: Washington, DC, 1984.
(104) Choudhury, D.; Sahu, J. K.; Sharma, G. D. Moisture sorption
isotherms, heat of sorption and properties of sorbed water of raw
bamboo (Dendrocalamus longispathus) shoots. Ind. Crops Prod. 2011,
33 (1), 211−216.
(105) Arslan, N.; Toğrul, H. Moisture Sorption Isotherms for Crushed
Chillies. Biosys. Eng. 2005, 90 (1), 47−61.
(106) Moreno, R.; Antolín, G.; Reyes, A.; Alvarez, P. Drying
Characteristics of Forest Biomass Particles of Pinus radiata. Biosys.
Eng. 2004, 88 (1), 105−115.
(107) Sahin, S.; Sumnu, S. G. Water Activity and Sorption Properties
of Foods. In Physical Properties of Foods; Springer: New York, 2006; pp
193−228, DOI: 10.1007/0-387-30808-3.
(108) Bell, L. N.; Labuza, T. P. Moisture Sorption: Practical Aspects of
Isotherm Measurement and Use; American Association of Cereal
Chemists, 1984.
(109) Gal, S., Recent Developments in Techniques for Obtaining
Complete Sorption Isotherms. In Water Activity: Influences on Food
Quality; Rockland, L. B., Stewart, G. F., Eds.; Academic Press, 1981; pp
89−110, DOI: 10.1016/B978-0-12-591350-8.50009-7.
(110) Tang, L.; Huang, B.; Yang, N.; Li, T.; Lu, Q.; Lin, W.; Chen, X.
Organic solvent-free and efficient manufacture of functionalized
cellulose nanocrystals via one-pot tandem reactions. Green Chem.
2013, 15 (9), 2369−2373.
(111) Zhang, Z.; Zhu, M.; Zhang, D. A Thermogravimetric study of
the characteristics of pyrolysis of cellulose isolated from selected
biomass. Appl. Energy 2018, 220, 87−93.
(112) Goodhew, P. J.; Humphreys, J.; Beanland, R. Electron
Microscopy and Analysis, 3th ed.; Taylor & Francis: London, 2001.
(113) Ciesielski, P. N.; Wang, W.; Chen, X. W.; Vinzant, T. B.; Tucker,
M. P.; Decker, S. R.; Himmel, M. E.; Johnson, D. K.; Donohoe, B. S.
Effect of mechanical disruption on the effectiveness of three reactors
used for dilute acid pretreatment of corn stover Part 2: morphological
and structural substrate analysis. Biotechnol. Biofuels 2014, 7, 47.
(114) Thygesen, A.; Oddershede, J.; Lilholt, H.; Thomsen, A. B.;
Ståhl, K. On the determination of crystallinity and cellulose content in
plant fibres. Cellulose 2005, 12 (6), 563.
(115) Meshitsuka, G.; Isogai, A. Chemical Structures of Cellulose,
Hemicellulose and Lignin; Marcel Dekker, Inc.: New York, 1996; p 11−-
34.
(116) Zhang, L.-h.; Li, D.; Wang, L.-j.; Wang, T.-p.; Zhang, L.; Chen,
X. D.; Mao, Z.-H. Effect of steam explosion on biodegradation of lignin
in wheat straw. Bioresour. Technol. 2008, 99 (17), 8512−8515.
(117) Segal, L.; Creely, J. J.; Martin, A. E.; Conrad, C. M. An Empirical
Method for Estimating the Degree of Crystallinity of Native Cellulose
Using the X-Ray Diffractometer. Text. Res. J. 1959, 29 (10), 786−794.
(118) Ruland, W. X-ray determination of crystallinity and diffuse
disorder scattering. Acta Crystallogr. 1961, 14 (11), 1180−1185.
(119) Rietveld, H. Line profiles of neutron powder-diffraction peaks
for structure refinement. Acta Crystallogr. 1967, 22 (1), 151−152.
(120) Debye, P. Zerstreuung von Röntgenstrahlen. Ann. Phys. 1915,
351 (6), 809−823.
(121) Zheng, Q.; Zhou, T.; Wang, Y.; Cao, X.; Wu, S.; Zhao, M.;
Wang, H.; Xu, M.; Zheng, B.; Zheng, J.; Guan, X. Pretreatment of wheat
straw leads to structural changes and improved enzymatic hydrolysis.
Sci. Rep. 2018, 8 (1), 1321.
(122) Mooney, C. A.; Mansfield, S. D.; Touhy, M. G.; Saddler, J. N.
The effect of initial pore volume and lignin content on the enzymatic
hydrolysis of softwoods. Bioresour. Technol. 1998, 64 (2), 113−119.
https://dx.doi.org/10.1021/acssuschemeng.9b06263
ACS Sustainable Chem. Eng. 2020, 8, 8059−8085
ACS Sustainable Chemistry & Engineering
(123) Fan, L. T.; Lee, Y.-H.; Beardmore, D. H. Mechanism of the
enzymatic hydrolysis of cellulose: Effects of major structural features of
cellulose on enzymatic hydrolysis. Biotechnol. Bioeng. 1980, 22 (1),
177−199.
(124) Gharpuray, M. M.; Lee, Y.-H.; Fan, L. T. Structural modification
of lignocellulosics by pretreatments to enhance enzymatic hydrolysis.
Biotechnol. Bioeng. 1983, 25 (1), 157−172.
(125) Bai, L.; Greca, L. G.; Xiang, W.; Lehtonen, J.; Huan, S.;
Nugroho, R. W. N.; Tardy, B. L.; Rojas, O. J. Adsorption and Assembly
of Cellulosic and Lignin Colloids at Oil/Water Interfaces. Langmuir
2019, 35 (3), 571−588.
(126) Hill, J.; Nelson, E.; Tilman, D.; Polasky, S.; Tiffany, D.
Environmental, economic, and energetic costs and benefits of biodiesel
and ethanol biofuels. Proc. Natl. Acad. Sci. U. S. A. 2006, 103 (30),
11206−11210.
(127) Asadullah, M. Barriers of commercial power generation using
biomass gasification gas: A review. Renewable Sustainable Energy Rev.
2014, 29, 201−215.
(128) Biorenewables Education Laboratory. Biomass Properties and
Handling. http://www.engineering.iastate.edu/brl/files/2011/10/
brl_biomassppop_instructor.pdf (accessed Dec 1, 2019).
(129) Enes, T.; Aranha, J.; Fonseca, T.; Lopes, D.; Alves, A.; Lousada,
J. Thermal Properties of Residual Agroforestry Biomass of Northern
Portugal. Energies 2019, 12 (8), 1418.
(130) Gardner, J. L.; He, W.; Li, C.; Wong, J.; Sale, K. L.; Simmons, B.
A.; Singh, S.; Tanjore, D. Calorimetric evaluation indicates that lignin
conversion to advanced biofuels is vital to improving energy yields. RSC
Adv. 2015, 5 (63), 51092−51101.
(131) Stickel, J. J.; Knutsen, J. S.; Liberatore, M. W.; Luu, W.;
Bousfield, D. W.; Klingenberg, D. J.; Scott, C. T.; Root, T. W.; Ehrhardt,
M. R.; Monz, T. O. Rheology measurements of a biomass slurry: an
inter-laboratory study. Rheol. Acta 2009, 48, 1005.
(132) Coffman, P.; McCaffrey, N.; Gardner, J.; Bhagia, S.; Kumar, R.;
Wyman, C. E.; Tanjore, D. In Situ Rheological Method to Evaluate
Feedstock Physical Properties Throughout Enzymatic Deconstruction.
Front. Energy Res. 2018, 6 (53), na DOI: 10.3389/fenrg.2018.00053.
(133) Samaniuk, J. R.; Scott, C. T.; Root, T. W.; Klingenberg, D. J.
Rheological modification of corn stover biomass at high solids
concentrations. J. Rheol. 2012, 56 (3), 649−665.
(134) Stickel, J. J.; Knutsen, J. S.; Liberatore, M. W.; Luu, W.;
Bousfield, D. W.; Klingenberg, D. J.; Scott, C. T.; Root, T. W.; Ehrhardt,
M. R.; Monz, T. O. Rheology measurements of a biomass slurry: an
inter-laboratory study. Rheol. Acta 2009, 48 (9), 1005−1015.
(135) Roche, C. M.; Dibble, C. J.; Knutsen, J. S.; Stickel, J. J.;
Liberatore, M. W. Particle concentration and yield stress of biomass
slurries during enzymatic hydrolysis at high-solids loadings. Biotechnol.
Bioeng. 2009, 104 (2), 290−300.
(136) Lynd, L. R. Overview and Evaluation of Fuel Ethanol from
Cellulosic Biomass: Technology, Economics, the Environment, and
Policy. Annu. Rev. Energy Env. 1996, 21 (1), 403−465.
(137) Wingren, A.; Galbe, M.; Zacchi, G. Techno-economic
evaluation of producing ethanol from softwood: Comparison of SSF
and SHF and identification of bottlenecks. Biotechnol. Prog. 2003, 19
(4), 1109−1117.
(138) Klingenberg, D. J.; Root, T. W.; Burlawar, S.; Scott, C. T.;
Bourne, K. J.; Gleisner, R.; Houtman, C.; Subramaniam, V. Rheometry
of coarse biomass at high temperature and pressure. Biomass Bioenergy
2017, 99, 69−78.
(139) Ehrhardt, M. R.; Monz, T. O.; Root, T. W.; Connelly, R. K.;
Scott, C. T.; Klingenberg, D. J. Rheology of Dilute Acid Hydrolyzed
Corn Stover at High Solids Concentration. Appl. Biochem. Biotechnol.
2010, 160 (4), 1102−1115.
(140) Rosgaard, L.; Andric, P.; Dam-Johansen, K.; Pedersen, S.;
Meyer, A. S. Effects of Substrate Loading on Enzymatic Hydrolysis and
Viscosity of Pretreated Barley Straw. Appl. Biochem. Biotechnol. 2007,
143 (1), 27−40.
(141) Um, B.-H.; Hanley, T. R. A Comparison of Simple Rheological
Parameters and Simulation Data for Zymomonas mobilis Fermentation
8081
pubs.acs.org/journal/ascecg Perspective
Broths with High Substrate Loading in a 3-L Bioreactor. Appl. Biochem.
Biotechnol. 2008, 145 (1), 29−38.
(142) Vaezi, M.; Kumar, A. Pipeline hydraulic transport of biomass
materials: A review of experimental programs, empirical correlations,
and economic assessments. Biomass Bioenergy 2015, 81, 70−82.
(143) Crawford, N. C.; Nagle, N.; Sievers, D. A.; Stickel, J. J. The
effects of physical and chemical preprocessing on the flowability of corn
stover. Biomass Bioenergy 2016, 85, 126−134.
(144) Samaniuk, J. R.; Tim Scott, C.; Root, T. W.; Klingenberg, D. J.
The effect of high intensity mixing on the enzymatic hydrolysis of
concentrated cellulose fiber suspensions. Bioresour. Technol. 2011, 102
(6), 4489−4494.
(145) Viamajala, S.; McMillan, J. D.; Schell, D. J.; Elander, R. T.
Rheology of corn stover slurries at high solids concentrations − Effects
of saccharification and particle size. Bioresour. Technol. 2009, 100 (2),
925−934.
(146) Pimenova, N. V.; Hanley, T. R. Measurement of Rheological
Properties of Corn Stover Suspensions. Appl. Biochem. Biotechnol. 2003,
106, 383−392.
(147) Knutsen, J. S.; Liberatore, M. W. Rheology of high-solids
biomass slurries for biorefinery applications. J. Rheol. 2009, 53 (4),
877−892.
(148) Dalpke, B.; Kerekes, R. J. The influence of fibre properties on
the apparent yield stress of flocculated pulp suspensions. J. Pulp Pap. Sci.
2005, 31 (1), 39−43.
(149) Ueki, Y.; Torigoe, T.; Ono, H.; Yoshiie, R.; Kihedu, J. H.;
Naruse, I. Gasification characteristics of woody biomass in the packed
bed reactor. Proc. Combust. Inst. 2011, 33 (2), 1795−1800.
(150) Dahlquist, E. Biomass as Energy Source: Resources, Systems and
Applications; CRC Press, 2013, DOI: 10.1201/b14513.
(151) Lumay, G.; Boschini, F.; Traina, K.; Bontempi, S.; Remy, J. C.;
Cloots, R.; Vandewalle, N. Measuring the flowing properties of powders
and grains. Powder Technol. 2012, 224, 19−27.
(152) Rouse, P. Comparison of Methods for the Measurement of the
Angle of Repose of Granular Materials. Geotech. Test. J. 2014, 37 (1),
164−168.
(153) Szalay, A.; Kelemen, A.; Pintye-Hódi, K. The influence of the
cohesion coefficient (C) on the flowability of different sorbitol types.
Chem. Eng. Res. Des. 2015, 93, 349−354.
(154) Jenike, A. W. Storage and Flow of Solids; University of Utah: Salt
Lake City, UT, 1964.
(155) Bodhmage, A. K. Correlation between Physical Properties and
Flowability Indicators for Fine Powders. Ph.D. Thesis, University of
Saskatchewan Saskatoon, Saskatchewan, 2006.
(156) Olatunde, G; Fasina, O; McDonald, T; Adhikari, S; Duke, S
Moisture effect on fluidization behavior of loblolly pine Wood grinds.
Biomass Convers. Biorefin. 2017, 7 (2), 207−220.
(157) van der Stelt, M. J. C.; Gerhauser, H.; Kiel, J. H. A.; Ptasinski, K.
J. Biomass upgrading by torrefaction for the production of biofuels: A
review. Biomass Bioenergy 2011, 35 (9), 3748−3762.
(158) Lin, Z.; Huang, H.; Zhang, H.; Zhang, L.; Yan, L.; Chen, J. Ball
Milling Pretreatment of Corn Stover for Enhancing the Efficiency of
Enzymatic Hydrolysis. Appl. Biochem. Biotechnol. 2010, 162 (7), 1872−
1880.
(159) Jiang, J.; Wang, J.; Zhang, X.; Wolcott, M. Assessing multi-scale
deconstruction of wood cell wall subjected to mechanical milling for
enhancing enzymatic hydrolysis. Ind. Crops Prod. 2017, 109, 498−508.
(160) Gibson, L. J. The hierarchical structure and mechanics of plant
materials. J. R. Soc., Interface 2012, 9 (76), 2749−2766.
(161) Al-Zube, L.; Sun, W.; Robertson, D.; Cook, D. The elastic
modulus for maize stems. Plant Methods 2018, 14 (1), 11.
(162) Robertson, D. J.; Julias, M.; Lee, S. Y.; Cook, D. D. Maize Stalk
Lodging: Morphological Determinants of Stalk Strength. Crop Sci.
2017, 57, 926−934.
(163) Wright, C. T.; Pryfogle, P. A.; Stevens, N. A.; Steffler, E. D.;
Hess, J. R.; Ulrich, T. H. Biomechanics of wheat/barley straw and corn
stover. Appl. Biochem. Biotechnol. 2005, 121 (1), 5−19.
(164) Charrier, A. M.; Lereu, A. L.; Farahi, R. H.; Davison, B. H.;
Passian, A. Nanometrology of Biomass for Bioenergy: The Role of
https://dx.doi.org/10.1021/acssuschemeng.9b06263
ACS Sustainable Chem. Eng. 2020, 8, 8059−8085
ACS Sustainable Chemistry & Engineering
Atomic Force Microscopy and Spectroscopy in Plant Cell Character-
ization. Front. Energy Res. 2018, 6 (11), na DOI: 10.3389/
fenrg.2018.00011.
(165) Himmel, M.; Tucker, M.; Baker, J.; Rivard, C.; Oh, K.;
Grohmann, K. Comminution of Biomass: Hammer and Knife Mills. In
Proceedings of the 7th Symposium on Biotechnology for Fuels and
Chemicals; Scott, C. D., Ed.; John Wiley, Tennessee, 1986, pp 39−58.
(166) Cadoche, L.; López, G. D. Assessment of size reduction as a
preliminary step in the production of ethanol from lignocellulosic
wastes. Biol. Wastes 1989, 30 (2), 153−157.
(167) Brandt, A.; Erickson, J. K.; Hallett, J. P.; Murphy, R. J.; Potthast,
A.; Ray, M. J.; Rosenau, T.; Schrems, M.; Welton, T. Soaking of pine
wood chips with ionic liquids for reduced energy input during grinding.
Green Chem. 2012, 14 (4), 1079−1085.
(168) Kokko, L.; Tolvanen, H.; Hämäläinen, K.; Raiko, R. Comparing
the energy required for fine grinding torrefied and fast heat treated pine.
Biomass Bioenergy 2012, 42, 219−223.
(169) Dooley, J. H.; Lanning, D. N.; Lanning, C. J. Woody biomass
size reduction with selective material orientation. Biofuels 2013, 4 (1),
35−43.
(170) Igathinathane, C.; Womac, A. R.; Sokhansanj, S.; Narayan, S.
Size reduction of high- and low-moisture corn stalks by linear knife grid
system. Biomass Bioenergy 2009, 33 (4), 547−557.
(171) Sluiter, A. Determination of Structural Carbohydrates and Lignin
in Biomass: Laboratory Analytical Procedure (LAP); NREL/TP-510-
42618; National Renewable Energy Laboratory: Golden, CO, 2008.
(172) Bu, L.; Xing, Y.; Yu, H.; Gao, Y.; Jiang, J. Comparative study of
sulfite pretreatments for robust enzymatic saccharification of corn cob
residue. Biotechnol. Biofuels 2012, 5 (1), 87.
(173) Presser, K. A.; Ratkowsky, D. A.; Ross, T. Modelling the growth
rate of Escherichia coli as a function of pH and lactic acid concentration.
Appl. Environ. Microbiol. 1997, 63 (6), 2355−2360.
(174) Groenewold, G. S.; Hodges, B.; Hoover, A. N.; Li, C.; Zarzana,
C. A.; Rigg, K.; Ray, A. E. Signatures of Biologically Driven
Hemicellulose Modification Quantified by Analytical Pyrolysis
Coupled with Multidimensional Gas Chromatography Mass Spec-
trometry. ACS Sustainable Chem. Eng. 2020, 8 (4), 1989−1997.
(175) Groenewold, G. S.; Johnson, K. M.; Fox, S. C.; Rae, C.; Zarzana,
C. A.; Kersten, B. R.; Rowe, S. M.; Westover, T. L.; Gresham, G. L.;
Emerson, R. M.; Hoover, A. N. Pyrolysis Two-Dimensional GC-MS of
Miscanthus Biomass: Quantitative Measurement Using an Internal
Standard Method. Energy Fuels 2017, 31 (2), 1620−1630.
(176) Cosgrove, D. J. ASSEMBLY AND ENLARGEMENT OF THE
PRIMARY CELL WALL IN PLANTS. Annu. Rev. Cell Dev. Biol. 1997,
13 (1), 171−201.
(177) Himmel, M. E.; Ding, S.-Y.; Johnson, D. K.; Adney, W. S.;
Nimlos, M. R.; Brady, J. W.; Foust, T. D. Biomass recalcitrance:
engineering plants and enzymes for biofuels production. Science 2007,
315 (5813), 804.
(178) Pattathil, S.; Avci, U.; Miller, J. S.; Hahn, M. G. Immunological
Approaches to Plant Cell Wall and Biomass Characterization: Glycome
Profiling. In Biomass Conversion: Methods and Protocols; Himmel, M. E.,
Ed.;Humana Press: Totowa, NJ, 2012; pp 61−72, DOI: 10.1007/978-
1-61779-956-3_6.
(179) Crowe, J. D.; Feringa, N.; Pattathil, S.; Merritt, B.; Foster, C.;
Dines, D.; Ong, R. G.; Hodge, D. B. Identification of developmental
stage and anatomical fraction contributions to cell wall recalcitrance in
switchgrass. Biotechnol. Biofuels 2017, 10 (1), 184.
(180) Pattathil, S.; Ingwers, M. W.; Victoriano, O. L.; Kandemkavil, S.;
McGuire, M. A.; Teskey, R. O.; Aubrey, D. P. Cell Wall Ultrastructure
of Stem Wood, Roots, and Needles of a Conifer Varies in Response to
Moisture Availability. Front. Plant Sci. 2016, 7 (882), na DOI: 10.3389/
fpls.2016.00882.
(181) De Diego, N.; Sampedro, M. C.; Barrio, R. J.; Saiz-Fernández, I.;
Moncaleán, P.; Lacuesta, M. Solute accumulation and elastic modulus
changes in six radiata pine breeds exposed to drought. Tree Physiol.
2013, 33 (1), 69−80.
(182) Miller, C. Chemical Principles of near Infrared Technology. In
Near Infrared Technology in the Agricultural and Food industries;
8082
pubs.acs.org/journal/ascecg Perspective
Williams, P, Norris, K, Eds.; American Association of Cereal Chemists,
Inc.: St. Paul, MN, USA, 2001; pp 19−37.
(183) Moore, A. K.; Owen, N. L. Infrared spectroscopic studies of
solid wood. Appl. Spectrosc. Rev. 2001, 36 (1), 65−86.
(184) Xu, H.; Li, B.; Mu, X.; Yu, G.; Liu, C.; Zhang, Y.; Wang, H.
Quantitative characterization of the impact of pulp refining on
enzymatic saccharification of the alkaline pretreated corn stover.
Bioresour. Technol. 2014, 169, 19−26.
(185) Gierlinger, N.; Goswami, L.; Schmidt, M.; Burgert, I.; Coutand,
C.; Rogge, T.; Schwanninger, M. In Situ FT-IR Microscopic Study on
Enzymatic Treatment of Poplar Wood Cross-Sections. Biomacromole-
cules 2008, 9 (8), 2194−2201.
(186) Thygesen, L. G. Determination of Dry Matter Content and
Basic Density of Norway Spruce by near Infrared Reflectance and
Transmittance Spectroscopy. J. Near Infrared Spectrosc. 1994, 2 (3),
127−135.
(187) Kelley, S. S.; Rials, T. G.; Snell, R.; Groom, L. H.; Sluiter, A. Use
of near infrared spectroscopy to measure the chemical and mechanical
properties of solid wood. Wood Sci. Technol. 2004, 38 (4), 257−276.
(188) Lestander, T. A.; Rhén, C. Multivariate NIR spectroscopy
models for moisture, ash and calorific content in biofuels using bi-
orthogonal partial least squares regression. Analyst 2005, 130 (8),
1182−1189.
(189) Yan, J.; Kiemle, D.; Liu, S. Quantification of xylooligomers in
hot water wood extract by 1H−13C heteronuclear single quantum
coherence NMR. Carbohydr. Polym. 2015, 117 (0), 903−909.
(190) Ralph, J. L., Landucci, L. L. NMR of Lignins. In Lignin and
Lignans: Advances in Chemistry; Heitner, C., Dimmel, D., Schmidt, J. A.,
Eds.; Taylor & Francis: Boca Raton, FL, 2010; Chapter 5, pp 137−244.
(191) Agblevor, F. A.; Besler, S. Inorganic Compounds in Biomass
Feedstocks. 1. Effect on the Quality of Fast Pyrolysis Oils. Energy Fuels
1996, 10 (2), 293−298.
(192) Lacey, J. A.; Aston, J. E.; Thompson, V. S. Wear Properties of
Ash Minerals in Biomass. Front. Energy Res. 2018, 6, 1−6.
(193) Sievers, D. A.; Kuhn, E. M.; Thompson, V. S.; Yancey, N. A.;
Hoover, A. N.; Resch, M. G.; Wolfrum, E. J. Throughput, Reliability,
and Yields of a Pilot-Scale Conversion Process for Production of
Fermentable Sugars from Lignocellulosic Biomass: A Study on
Feedstock Ash and Moisture. ACS Sustainable Chem. Eng. 2020, 8
(4), 2008−2015.
(194) Leal, J. H.; Torres, E. L.; Rouse, W. T.; Moore, C. M.; Sutton, A.
D.; Hoover, A. N.; Li, C.; Resch, M. G.; Donohoe, B. S.; Ray, A. E.;
Semelsberger, T. A. Impacts of Inorganic Material (Total Ash) on
Surface Energy, Wettability, and Cohesion of Corn Stover. ACS
Sustainable Chem. Eng. 2020, 8 (4), 2061−2072.
(195) Bonner, I. J.; Smith, W. A.; Einerson, J. J.; Kenney, K. L. Impact
of Harvest Equipment on Ash Variability of Baled Corn Stover Biomass
for Bioenergy. BioEnergy Res. 2014, 7 (3), 845−855.
(196) Banks, S. W.; Nowakowski, D. J.; Bridgwater, A. V. Impact of
Potassium and Phosphorus in Biomass on the Properties of Fast
Pyrolysis Bio-oil. Energy Fuels 2016, 30 (10), 8009−8018.
(197) Fahmi, R.; Bridgwater, A. V.; Donnison, I.; Yates, N.; Jones, J.
M. The effect of lignin and inorganic species in biomass on pyrolysis oil
yields, quality and stability. Fuel 2008, 87 (7), 1230−1240.
(198) Vassilev, S. V.; Vassileva, C. G. Water-Soluble Fractions of
Biomass and Biomass Ash and Their Significance for Biofuel
Application. Energy Fuels 2019, 33 (4), 2763−2777.
(199) Sluiter, A.; Hames, B.; Ruiz, R.; Scarlata, C.; Sluiter, J.;
Templeton, D. Determination of Ash in Biomass; National Renewable
Energy Laboratory, 2005.
(200) Westover, T. L.; Emerson, R. M. Rapid Analysis of Inorganic
Species in Herbaceous Materials Using Laser-Induced Breakdown
Spectroscopy. Ind. Biotechnol. 2015, 11 (6), 322−330.
(201) Xiao, L.; Wei, H.; Himmel, M. E.; Jameel, H.; Kelley, S. S. NIR
and Py-mbms coupled with multivariate data analysis as a high-
throughput biomass characterization technique: a review. Front. Plant
Sci. 2014, 5 (388), na DOI: 10.3389/fpls.2014.00388.
(202) Morgan, T. J.; George, A.; Boulamanti, A. K.; Á lvarez, P.;
Adanouj, I.; Dean, C.; Vassilev, S. V.; Baxter, D.; Andersen, L. K.
https://dx.doi.org/10.1021/acssuschemeng.9b06263
ACS Sustainable Chem. Eng. 2020, 8, 8059−8085
ACS Sustainable Chemistry & Engineering
Quantitative X-ray Fluorescence Analysis of Biomass (Switchgrass,
Corn Stover, Eucalyptus, Beech, and Pine Wood) with a Typical
Commercial Multi-Element Method on a WD-XRF Spectrometer.
Energy Fuels 2015, 29 (3), 1669−1685.
(203) Thyrel, M.; Aulin, R.; Lestander, T. A. A method for
differentiating between exogenous and naturally embedded ash in
bio-based feedstock by combining ED-XRF and NIR spectroscopy.
Biomass Bioenergy 2019, 122, 84−89.
(204) Clark, D. H.; Mayland, H. F.; Lamb, R. C. Mineral Analysis of
Forages with near Infrared Reflectance Spectroscopy. Agron. J. 1987,
79, 485−490.
(205) Huang, C.; Han, L.; Yang, Z.; Liu, X. Exploring the use of near
infrared reflectance spectroscopy to predict minerals in straw. Fuel
2009, 88 (1), 163−168.
(206) Bruun, S.; Jensen, J. W.; Magid, J.; Lindedam, J.; Engelsen, S. B.
Prediction of the degradability and ash content of wheat straw from
different cultivars using near infrared spectroscopy. Ind. Crops Prod.
2010, 31 (2), 321−326.
(207) Cozzolino, D.; Moron, A. Exploring the use of near infrared
reflectance spectroscopy (NIRS) to predict trace minerals in legumes.
Anim. Feed Sci. Technol. 2004, 111 (1), 161−173.
(208) Lestander, T. A.; Johnsson, B.; Grothage, M. NIR techniques
create added values for the pellet and biofuel industry. Bioresour.
Technol. 2009, 100 (4), 1589−1594.
(209) Lee, K.; Roy, S.; Cakmak, E.; Lacey, J. A.; Watkins, T. R.; Meyer,
H. M.; Thompson, V. S.; Keiser, J. R.; Qu, J. Composition-Preserving
Extraction and Characterization of Biomass Extrinsic and Intrinsic
Inorganic Compounds. ACS Sustainable Chem. Eng. 2020, 8 (3), 1599−
1610.
(210) Tian, X.; Zhang, H.; Sheng, C. Self-Heating of Agricultural
Residues During Storage and Its Impact on Fuel Properties. Energy
Fuels 2018, 32 (4), 4227−4236.
(211) Donohoe, B. S.; Decker, S. R.; Tucker, M. P.; Himmel, M. E.;
Vinzant, T. B. Visualizing lignin coalescence and migration through
maize cell walls following thermochemical pretreatment. Biotechnol.
Bioeng. 2008, 101 (5), 913−925.
(212) Zeng, Y.; Zhao, S.; Yang, S.; Ding, S.-Y. Lignin plays a negative
role in the biochemical process for producing lignocellulosic biofuels.
Curr. Opin. Biotechnol. 2014, 27, 38−45.
(213) Ishizawa, C. I.; Jeoh, T.; Adney, W. S.; Himmel, M. E.; Johnson,
D. K.; Davis, M. F. J. C. Can delignification decrease cellulose
digestibility in acid pretreated corn stover? Cellulose 2009, 16 (4), 677−
686.
(214) Zeng, Y.; Donohoe, B. S. Lignin Visualization: Advanced
Microscopy Techniques for Lignin Characterization. In Lignin
Valorization: Emerging Approaches; Beckham, G. T., Ed.; RCS
Publishing, 2018, DOI: 10.1039/9781788010351-00477.
(215) Himmelsbach, D. S.; Akin, D. E. Near-Infrared Fourier-
Transform Raman Spectroscopy of Flax (Linum usitatissimum L.)
Stems. J. Agric. Food Chem. 1998, 46 (3), 991−998.
(216) Schrader, B.; Klump, H. H.; Schenzel, K.; Schulz, H. Non-
destructive NIR FT Raman analysis of plants. J. Mol. Struct. 1999, 509
(1), 201−212.
(217) Zeng, Y.; Saar, B. G.; Friedrich, M. G.; Chen, F.; Liu, Y.-S.;
Dixon, R. A.; Himmel, M. E.; Xie, X. S.; Ding, S.-Y. J. B. R. Imaging
lignin-downregulated alfalfa using coherent anti-Stokes Raman
scattering microscopy. BioEnergy Res. 2010, 3 (3), 272−277.
(218) Saar, B. G.; Zeng, Y.; Freudiger, C. W.; Liu, Y.-S.; Himmel, M.
E.; Xie, X. S.; Ding, S.-Y. Label-free, real-time monitoring of biomass
processing with stimulated Raman scattering microscopy. Angew.
Chem., Int. Ed. 2010, 49 (32), 5476−5479.
(219) Zeng, Y.; Himmel, M. E.; Ding, S.-Y. J. B. f. b. Visualizing
chemical functionality in plant cell walls. Biotechnol. Biofuels 2017, 10
(1), 263.
(220) Zeng, Y.; Yarbrough, J. M.; Mittal, A.; Tucker, M. P.; Vinzant, T.
B.; Decker, S. R.; Himmel, M. E. J. B. f. b. In situ label-free imaging of
hemicellulose in plant cell walls using stimulated Raman scattering
microscopy. Biotechnol. Biofuels 2016, 9 (1), 256.
8083
pubs.acs.org/journal/ascecg Perspective
(221) Zeng, Y.; Zhao, S.; Wei, H.; Tucker, M. P.; Himmel, M. E.;
Mosier, N. S.; Meilan, R.; Ding, S.-Y. J. B. f. b. In situ micro-
spectroscopic investigation of lignin in poplar cell walls pretreated by
maleic acid. Biotechnol. Biofuels 2015, 8 (1), 126.
(222) Mohammadi-Jam, S.; Waters, K. E. Inverse gas chromatography
applications: A review. Adv. Colloid Interface Sci. 2014, 212, 21−44.
(223) Butler, D.; Williams, D. R. Particulate Characterization: Inverse
Gas Chromatography. In Encyclopedia of Separation Science; Wilson, I.
D., Ed.; Academic Press: Oxford, 2000; pp 3609−3614, DOI: 10.1016/
B0-12-226770-2/07451-2.
(224) Grimsey, I. M.; Feeley, J. C.; York, P. Analysis of the surface
energy of pharmaceutical powders by inverse gas chromatography. J.
Pharm. Sci. 2002, 91 (2), 571−583.
(225) Converse, A. O.; Ooshima, H.; Burns, D. S. Kinetics of
enzymatic hydrolysis of lignocellulosic materials based on surface area
of cellulose accessible to enzyme and enzyme adsorption on lignin and
cellulose. Appl. Biochem. Biotechnol. 1990, 24 (1), 67.
(226) Zu, S.; Li, W.-z.; Zhang, M.; Li, Z.; Wang, Z.; Jameel, H.; Chang,
H.-m. Pretreatment of corn stover for sugar production using dilute
hydrochloric acid followed by lime. Bioresour. Technol. 2014, 152, 364−
370.
(227) Akgül, M.; Korkut, S.; Ç amlibel, O.; Candan, Z.; Akbulut, T.
Wettability and Surface Roughness Characteristics of Medium Density
Fiberboard Panels from Rhododendron (Rhododendron Ponticum)
Biomass. Cienc. y Tecnol. 2012, 14 (2), 185−193.
(228) Notley, S. M.; Norgren, M. Surface Energy and Wettability of
Spin-Coated Thin Films of Lignin Isolated from Wood. Langmuir 2010,
26 (8), 5484−5490.
(229) Harmsen, P.; Huijgen, W.; Bermudez, L.; Bakker, R.; López, L.;
Bakker, R. Literature Review of Physical and Chemical Pretreatment
Processes for Lignocellulosic Biomass; Wageningen UR Food & Biobased
Research, 2010.
(230) Voelkel, A.; Strzemiecka, B.; Adamska, K.; Milczewska, K.
Inverse gas chromatography as a source of physiochemical data. J.
Chromatogr. 2009, 1216 (10), 1551−1566.
(231) Gamelas, J. A. F. The surface properties of cellulose and
lignocellulosic materials assessed by inverse gas chromatography: a
review. Cellulose 2013, 20 (6), 2675−2693.
(232) Etzler, F. M.; Lockwood, C. E. Characterization of Surface Free
Energies and Surface Chemistry of Solids; International Fine Particle
Research Institute, 2001.
(233) Butler, D.; Williams, D. R. Particulate Characterization: Inverse
Gas Chromatography. In Encyclopedia of Separation Science; Academic
Press, 2000; pp 3609−3614, DOI: 10.1016/B0-12-226770-2/07451-2
(234) Kondor, A.; Hogan, S. A. Relationships between surface energy
analysis and functional characteristics of dairy powders. Food Chem.
2017, 237, 1155−1162.
(235) Leal, J. H.; Moore, C. M.; Sutton, A. D.; Semelsberger, T. A.
Surface energy of air fractionated corn stover. Ind. Crops Prod. 2019,
137, 628−635.
(236) Mani, S.; Tabil, L. G.; Sokhansanj, S. Grinding performance and
physical properties of wheat and barley straws, corn stover and
switchgrass. Biomass Bioenergy 2004, 27 (4), 339−352.
(237) Taylor, J. B.; Carrano, A. L.; Kandlikar, S. G. Characterization of
the effect of surface roughness and texture on fluid flowpast, present,
and future. Int. J. Therm. Sci. 2006, 45 (10), 962−968.
(238) Shastri, Y.; Hansen, A.; Rodríguez, L.; Ting, K. C. Engineering
and Science of Biomass Feedstock Production and Provision; Springer,
2014; DOI: 10.1007/978-1-4899-8014-4.
(239) Barthlott, W.; Neinhuis, C. Purity of the sacred lotus, or escape
from contamination in biological surfaces. Planta 1997, 202 (1), 1−8.
(240) Wenzel, R. N. RESISTANCE OF SOLID SURFACES TO
WETTING BY WATER. Ind. Eng. Chem. 1936, 28 (8), 988−994.
(241) Yoshimitsu, Z.; Nakajima, A.; Watanabe, T.; Hashimoto, K.
Effects of Surface Structure on the Hydrophobicity and Sliding
Behavior of Water Droplets. Langmuir 2002, 18 (15), 5818−5822.
(242) Gallagher, S. R. Digital Image Processing and Analysis with
ImageJ. Current Protocols: Essential Laboratory Techniques 2014, 9 (1),
A.3C.1−A.3C.29.
https://dx.doi.org/10.1021/acssuschemeng.9b06263
ACS Sustainable Chem. Eng. 2020, 8, 8059−8085
ACS Sustainable Chemistry & Engineering
(243) Brocks, T.; Cioffi, M. O. H.; Voorwald, H. J. C. Effect of fiber
surface on flexural strength in carbon fabric reinforced epoxy
composites. Appl. Surf. Sci. 2013, 274, 210−216.
(244) Mohanaiah, P.; Sathyanarayana, P.; Gurukumar, L. Image
Texture Feature Extraction Using GLCM Approach. Int. J. Sci. Res. Publ.
2013, 3 (5), na.
(245) Pieniazek, F.; Messina, V. Scanning electron microscopy
combined with image processing technique: Microstructure and texture
analysis of legumes and vegetables for instant meal. Microsc. Res. Tech.
2016, 79 (4), 267−275.
(246) Webb, P. A. Volume and Density Determinations for Particle
Technologists; Micromeritics Instrument Corp., 2001.
(247) Jenike, A. W. Storage and Flow of Solids; Bulletin No. 123;
University of Utah: Salt Lake City, UT, 1976.
(248) Oyedeji, O.; Fasina, O. Impact of drying-grinding sequence on
loblolly pine chips preprocessing effectiveness. Ind. Crops Prod. 2017,
96, 8−15.
(249) Bernhart, M. E.; Fasina, O. Physical Properties and Pyrolysis
Behavior of Fractionated Poultry Litter; AGRIS, 2013, Vol. 52, Issue 2,
DOI: 10.13031/2013.26810.
(250) Ogden, C. A. Flow Mechanics of Switchgrass Bulk Solid in Hoppers
under Gravity Discharge. Ph.D. Thesis, Purdue University, West
Lafayette, IN, 2010.
(251) Compilation of ASTM Standard Definitions, 8th ed.; American
Society for Testing and Materials, 1994.
(252) British Standard BS 2955: Glossary of Terms Relating to Particle
Technology; British Standards Institution, 1991.
(253) Naimi, L.; Sokhansanj, S.; Bi, X.; Lim, J.; Melin, S. A Study on the
Impact of Wood Species on Grinding Performance; American Society of
Agricultural and Biological Engineers: Dallas, TX, 2012,
DOI: 10.13031/2013.42268.
(254) Falk, J. Particle and Feeding Characteristics of Biomass Powders.
Master’s Thesis, UMEA University, 2013.
(255) Tabil, L. G.; Sokhansanj, S. Bulk Properties of Alfalfa Grind in
Relation to Its Compaction Characteristics; AGRIS, 1997; Vol. 13, Issue 4,
DOI: 10.13031/2013.21618.
(256) Tumuluru, J. S.; Tabil, L. G.; Song, Y.; Iroba, K. L.; Meda, V.
Grinding energy and physical properties of chopped and hammer-
milled barley, wheat, oat, and canola straws. Biomass Bioenergy 2014, 60,
58−67.
(257) Adapa, P.; Tabil, L.; Schoenau, G. Physical and frictional
properties of non-treated and steam exploded barley, canola, oat and
wheat straw grinds. Powder Technol. 2010, 201 (3), 230−241.
(258) Chevanan, N.; Womac, A. R.; Bitra, V. S. P.; Igathinathane, C.;
Yang, Y. T.; Miu, P. I.; Sokhansanj, S. Bulk density and compaction
behavior of knife mill chopped switchgrass, wheat straw, and corn
stover. Bioresour. Technol. 2010, 101 (1), 207−214.
(259) Yang, Y. Image and Sieve Analysis of Biomass Particle Sizes and
Separation after Size Reduction. Master’s Thesis, University of
Tennessee, Knoxville, TN, 2007.
(260) Womac, A. R.; Igathinathane, C.; Sokhansanj, S.; Pordesimo, L.
O. Biomass moisture relations of an agricultural field residue: Corn
stover. Trans. ASAE 2005, 48 (6), 2073−2083.
(261) Hrncırová, M.; Pospıšil, J.; Š pilácek, M. Size Analysis of Solid
Particles Using Laser Diffraction and Sieve Analysis. J. Eng. Mech. 2013,
20 (3/4), 309−318.
(262) Carr, R. L. Evaluating Flow Properties of Solids. Arch.
Ophthalmol. 1965, 74, 163−168.
(263) Fayed, M. E.; Skocir, T. Mechanical Conveyors: Selection and
Operation, 1st ed.; CRC Press: Boca Raton, FL, 1996.
(264) Oyedeji, O.; Fasina, O.; Adhikari, S.; McDonald, T.; Taylor, S.
The effect of storage time and moisture content on grindability of
loblolly pine (Pinus taeda L.). Eur. J. Wood Prod. 2016, 74 (6), 857−
866.
(265) Naimi, L. J.; Collard, F.; Bi, X.; Lim, C. J.; Sokhansanj, S.
Development of size reduction equations for calculating power input
for grinding pine wood chips using hammer mill. Biomass Convers.
Biorefin. 2016, 6 (4), 397−405.
8084
pubs.acs.org/journal/ascecg Perspective
(266) Naimi, L.; Sokhansanj, S.; Bi, X.; Lim, J.; Womac, A.; Lau, A.;
Melin, S. Development of Size Reduction Equations for Calculating
Energy Input for Grinding Lignocellulosic Particles. Appl. Eng. Agric
2013, 29, 93−100.
(267) Bitra, V. S. P.; Womac, A. R.; Igathinathane, C.; Miu, P. I.; Yang,
Y. T.; Smith, D. R.; Chevanan, N.; Sokhansanj, S. Direct measures of
mechanical energy for knife mill size reduction of switchgrass, wheat
straw, and corn stover. Bioresour. Technol. 2009, 100 (24), 6578−6585.
(268) Bitra, V.; R. Womac, A.; Sokhansanj, S.; Igathinathane, C. Knife
Mill Comminution Energy Analysis of Switchgrass, Wheat Straw, and Corn
Stover and Characterization of Particle Size Distributions; AGRIS, 2010;
Vol. 53.
(269) Ghorbani, Z.; Masoumi, A. A.; Hemmat, A. Specific energy
consumption for reducing the size of alfalfa chops using a hammer mill.
Biosys. Eng. 2010, 105 (1), 34−40.
(270) Repellin, V.; Govin, A.; Rolland, M.; Guyonnet, R. Energy
requirement for fine grinding of torrefied wood. Biomass Bioenergy
2010, 34 (7), 923−930.
(271) Zhu, W.; Zhu, J. Y.; Gleisner, R.; Pan, X. On energy
consumption for size-reduction and yields from subsequent enzymatic
saccharification of pretreated lodgepole pine. Bioresour. Technol. 2010,
101, 2782−92.
(272) Moiceanu, G.; Paraschiv, G.; Voicu, G.; Dinca, M.; Negoita, O.;
Chitoiu, M.; Tudor, P. Energy Consumption at Size Reduction of
Lignocellulose Biomass for Bioenergy. Sustainability 2019, 11 (9),
2477.
(273) Faix, O. Classification of Lignins from Different Botanical
Origins by FT-IR Spectroscopy. Holzforschung 1991, 45 (1), 21−27.
(274) Schwanninger, M.; Rodrigues, J. C.; Pereira, H.; Hinterstoisser,
B. Effects of short-time vibratory ball milling on the shape of FT-IR
spectra of wood and cellulose. Vib. Spectrosc. 2004, 36 (1), 23.
(275) Xiao, B.; Sun, X. F.; Sun, R. Chemical, structural, and thermal
characterizations of alkali-soluble lignins and hemicelluloses, and
cellulose from maize stems, rye straw, and rice straw. Polym. Degrad.
Stab. 2001, 74 (2), 307−319.
(276) Himmelsbach, D. S.; Khalili, S.; Akin, D. E. The use of FT-IR
microspectroscopic mapping to study the effects of enzymatic retting of
flax (Linum usitatissimum L) stems. J. Sci. Food Agric. 2002, 82 (7),
685−696.
(277) Sills, D. L.; Gossett, J. M. Using FTIR to predict saccharification
from enzymatic hydrolysis of alkali-pretreated biomasses. Biotechnol.
Bioeng. 2012, 109 (2), 353−362.
(278) Vázquez, G.; Antorrena, G.; González, J.; Freire, S. FTIR, 1H
and 13C NMR Characterization of Acetosolv-Solubilized Pine and
Eucalyptus Lignins. Holzforschung 1997, 51, 158.
(279) Kačuráková, M.; Belton, P. S.; Wilson, R. H.; Hirsch, J.;
Ebringerová, A. Hydration properties of xylan-type structures: an FTIR
study of xylooligosaccharides. J. Sci. Food Agric. 1998, 77 (1), 38−44.
(280) Kubo, S.; Kadla, J. F. Hydrogen Bonding in Lignin: A Fourier
Transform Infrared Model Compound Study. Biomacromolecules 2005,
6 (5), 2815−2821.
(281) González-Sáiz, J. M.; Esteban-Díez, I.; Sánchez-Gallardo, C.;
Pizarro, C. Monitoring of substrate and product concentrations in
acetic fermentation processes for onion vinegar production by NIR
spectroscopy: value addition to worthless onions. Anal. Bioanal. Chem.
2008, 391 (8), 2937−2947.
(282) Philip Ye, X.; Liu, L.; Hayes, D.; Womac, A.; Hong, K.;
Sokhansanj, S. Fast classification and compositional analysis of
cornstover fractions using Fourier transform near-infrared techniques.
Bioresour. Technol. 2008, 99 (15), 7323−7332.
(283) Sun, R.; Lawther, J. M.; Banks, W. B. Fractional and structural
characterization of wheat straw hemicelluloses. Carbohydr. Polym.
1996, 29 (4), 325−331.
(284) Ebringerová, A.; Hromádková, Z.; Alföldi, J.; Berth, G.
Structural and solution properties of corn cob heteroxylans. Carbohydr.
Polym. 1992, 19 (2), 99−105.
(285) Imamura, T.; Watanabe, T.; Kuwahara, M.; Koshijima, T. Ester
linkages between lignin and glucuronic acid in lignin-carbohydrate
https://dx.doi.org/10.1021/acssuschemeng.9b06263
ACS Sustainable Chem. Eng. 2020, 8, 8059−8085
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Perspective

complexes from Fagus crenata. Phytochemistry 1994, 37 (4), 1165−

1173.
(286) Gabrielii, I.; Gatenholm, P.; Glasser, W. G.; Jain, R. K.; Kenne,
L. Separation, characterization and hydrogel-formation of hemi-
cellulose from aspen wood. Carbohydr. Polym. 2000, 43 (4), 367−374.

8085 https://dx.doi.org/10.1021/acssuschemeng.9b06263
ACS Sustainable Chem. Eng. 2020, 8, 8059−8085