Article

Cite This: Energy Fuels 2018, 32, 10683−10694 pubs.acs.org/EF

Integrated Particle- and Reactor-Scale Simulation of Pine Pyrolysis

in a Fluidized Bed
M. Brennan Pecha,† Emilio Ramirez,‡ Gavin M. Wiggins,‡ Daniel Carpenter,† Branden Kappes,§
Stuart Daw,‡ and Peter N. Ciesielski*,†
†
Biosciences Center, National Renewable Energy Laboratory, 1503 Denver West Parkway, Golden, Colorado 80401, United States
‡
Oak Ridge National Laboratory, 2360 Cherahala Boulevard, Knoxville, Tennessee 37932, United States
§
Department of Mechanical Engineering, Colorado School of Mines, 1500 Illinois Street, Golden, Colorado 80401, United States
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ABSTRACT: We report results from a multiscale computational modeling study of biomass fast pyrolysis in an experimental
laboratory reactor that combined the hydrodynamics predicted by a two-fluid model (TFM) with predictions from a finite
Downloaded via UNIV OF PRETORIA on September 3, 2019 at 09:59:16 (UTC).

element method (FEM) simulation of heat and mass transfer and chemical reactions within biomass particles. The experimental
pyrolyzer consisted of a 2 in. (5.1 cm) diameter bubbling fluidized bed reactor (FBR) fed with milled pine pellets. The
predicted FBR hydrodynamics included estimates of the residence times that the gas and biomass particles spend in the reactor
before they exit. A single-particle FEM simulation was constructed on the basis of the geometry and heat transfer properties
determined from optical and X-ray computed tomography measurements of wood and char particles collected from the
experimental FBR, along with previously proposed pyrolysis reaction kinetics. Taken together, the combined TFM and FEM
simulation results predicted net bio-oil yields at the reactor exit that agree well with experimental observations, without any
arbitrary fitting parameters. The combined computational models also provided practical information about the most important
reactor and feedstock parameters.

1. INTRODUCTION devoid of spatial parameters) have also been developed.10,11

Today, pyrolysis is recognized in the renewable energy sector
as a viable pathway for renewable biofuels, chemicals, and high-
value carbonaceous materials.1 Although the technology is very
popular, it is difficult to implement at industrial scales as a
result of the complex, heterogeneous nature of biomass
feedstocks and multiphase reactor operations.2 Nearly every
aspect of pyrolysis impacts the product yield temperature, heat
transfer mechanism, collection system, biomass composition
and microstructure, ash content, particle size, and others.3 The
goal of fast pyrolysis is to produce bio-oil via rapid heat transfer
(>100 °C s−1) to biomass particles (such as wood) in the
presence of an inert carrier gas, which quickly removes
condensable vapors and non-condensable product gases. Once
condensed, the vapors produce high yields of liquefied bio-oil.
Many different types of biomass pyrolysis reactors have been
proposed and tested over the years, but one of the most
common reactor designs used in laboratory studies is the
fluidized bed reactor (FBR), in which biomass particles are
injected into a preheated bed of denser particles (such as sand)
that are “fluidized” by an upward flowing gas into a state that is
similar to a boiling liquid.4 To determine optimal reactor
configurations and operating conditions, many researchers
have developed reasonable models to predict heat transfer,
chemical reactions, and mass transfer for this type of reactor,5,6
but often experimental correlations are used in scaleup as a
result of the complexity and unreliability of these models.
1.1. Challenges to Modeling Biomass Pyrolysis
Phenomena. There are essentially three length scales at
which pyrolysis models have been developed: the reactor
scale,7 the single-particle scale,8 and the chemical species level.9
Global or semi-global scale models (i.e., empirical kinetics
Global kinetic modeling is the simplest to perform because of
the lack of coupling to transport phenomena, which are critical
in determining process outcomes in many pyrolysis scenarios.
Coupling models of transport phenomena to detailed chemical
reaction mechanisms often require large computational
resources, which can surpass capabilities of current day high-
performance computing resources, although some progress has
been made recently with lumped-species mechanisms and
particle-scale physical models.12−14
1.2. Simulating Realistic Particle Geometries. Single-
particle models have emerged as a useful approach for studying
feedstock-specific effects and other physical phenomena
commonly observed in the laboratory. Given sufficient
feedstock characterization data, such as particle size, shape,
composition, density, and porosity, such models may be
parametrized for specific biomass feedstocks. This facilitates a
more accurate representation of the inherent biocomplexity
and heterogeneity of real biomass feedstocks and can thereby
account for species-specific variations in conversion out-
comes.15 In addition, modeling pyrolysis at the single-particle
level allows for insights into the interconnected phenomena of
heat transfer, mass transfer, and conversion kinetics in the
context of physically accurate geometries using well-studied
engineering approaches.
One of the most important findings from laboratory studies
of biomass fast pyrolysis is that the highest yields of bio-oil are
achieved when the feed particle size is less than 0.5 mm.16 For
Received: July 3, 2018
Revised: August 17, 2018
Published: September 4, 2018

© 2018 American Chemical Society 10683 DOI: 10.1021/acs.energyfuels.8b02309

Energy Fuels 2018, 32, 10683−10694
Energy & Fuels
each reactor, there is an optimal particle size that achieves the
highest yields within the respective operating envelope. It has
been proposed that this trend is due to the faster heat and mass
transfer rates that can be achieved with the relatively large
surface area/volume ratios of the smaller biomass particles.17,18
Similarly, as a result of the anisotropic exterior geometry,
which is typical of biomass particles, higher particle aspect
ratios (D/L) provide a higher yield of bio-oil.19
Recent technological advances have allowed for the use of X-
ray computed tomography (XCT) to characterize micrometer-
scale macroporosity in materials such as wood and char. While
the technique has been used for coal as early as 1996 (as
reviewed by Mathews et al.20), only recently has it been used
for biomass. The development of XCT, starting in the early
1970s,21 did not evolve to the low-micrometer resolution until
the late 1980s, when the use of the current scintillation-type
detector was coupled to a charge-coupled device to achieve
resolutions of 2.5 μm.22,23 Improvements in computing power,
lab source brilliance, and data collection techniques have
steadily improved the resolution of lab-scale XCT to 50 nm
(e.g., Zeiss Ultra series X-ray microscopes) and 350 nm (e.g.,
Zeiss Versa series X-ray microscopes). Hyväluoma et al.24 used
XCT to study porosity characteristics of various biochars,
finding that the pore size did not change dramatically with the
temperature but that the original properties of the biomass
were strong predictors of the properties of the char. Similar
findings were reported by Jones et al.25 XCT of chars from
gasification by Watanabe26 showed that they preserved the
same pore structure as the biomass starting material and that
this anisotropy forced reaction progression to primarily occur
along the direction of the grains rather than perpendicular to
them. Thus, it is critical to represent the anisotropic porosity
and permeability in pyrolysis simulations to realistically
represent experimental observations.
Biomass particles typically exhibit anisotropic exterior
geometries. In one early study, Di Blasi implemented a
model that includes particle multidimensional shrinking,
convection, conduction, and radiation, multistep kinetics, and
moisture evaporation.27 However, the kinetic scheme was not
well-verified. Bellais developed a cylinder model for slow
pyrolysis with secondary reactions but did not include gas
species.28 Another work studied the effect of the particle size
and aspect ratio on the yields of products from pyrolysis,
although it did not include water evaporation or mass transfer
by diffusion, and particle shrinking is not included.19 Paulsen et
al. developed an interesting model to track carbohydrate
degradation inside the particle but used an isotropic model,
ignored secondary reactions, and did not include diffusive mass
transfer.29 Some studies even hypothesized a liquid-phase
pyrolysis intermediate that bubbled as it vaporized.30−33
1.3. Multiscale Computational Fluid Dynamics (CFD)
Modeling Approach. Fluid bed pyrolyzers are commonly
used in laboratory and industrial settings to take advantage of
the constant flow of gas over all particles, which allows for high
heat transfer from gas to solids.4 The gas and solids mixing and
contacting patterns in FBRs are extremely complex. CFD
provides a way to simulate the spatiotemporal details about
pressures, velocities, flows, and concentrations that are either
impossible or extremely difficult to obtain experimentally.34
CFD has also been used in numerous studies of gas−solid
fluidized beds,35 but a very limited number of biomass fast
pyrolysis CFD studies have addressed hydrodynamic ef-
fects.7,36−39 It is generally not feasible to directly simulate
10684
Article
the motion of all of the individual particles in FBRs as a result
of limits of current computers and the high computational cost
of tracking the thousands or millions of particles present in
typical reactors. Thus, more approximate methods, such as the
two-fluid modeling (TFM) approach, have been pursued as a
way to reduce computational overhead.40 A recent TFM
modeling work illustrated the importance of using multiple
particle sizes for accurate pyrolysis conversion times, although
it did not account for intraparticle gradients.41 In addition,
recent reviews have detailed efforts to advance pyrolysis reactor
simulations,42,43 specifically methods for linking the physics
and chemistry at different spatial and temporal scales to
achieve the correct global reactor performance.44 However,
one remaining topic that has received little attention is the
mixing behavior of non-spherical biomass particles and their
residence times in FBRs.
In this work, we present a multiscale integration approach
similar to that previously employed by Wurzenburger and
colleagues,45 wherein reactor- and particle-scale modeling
approaches are combined to provide an approximate
description of the key physics and chemistry while reducing
the computational overhead. In this work, TFM predictions of
the hydrodynamics were used to estimate particle and gas
residence times, which were then combined with single-particle
simulations of realistic biomass particle evolution during
pyrolysis to estimate the overall yield of bio-oil for typical
laboratory FBR conditions. We expect that this type of
approach to integrated, multiscale modeling represents an
exemplar computational framework that will enable many types
of rapid screening simulations to estimate and interpret the
effects of key experimental pyrolyzer parameters, such as
geometry, carrier gas flow rate, temperature, and residence
times, and realistic biomass feedstock parameters, such as
species and size−shape distributions.
2. EXPERIMENTAL SECTION
2.1. Fluid Bed Pyrolyzer. The experimental 2 in. fluid bed reactor
(2FBR) at the National Renewable Energy Laboratory (NREL) was
used as the basis for the computational simulations of biomass fast
pyrolysis studied here. The key relevant features of this reactor are
illustrated in Figure 1. While the 2FBR is part of a more extensive
experimental research reactor system that includes two FBRs, an
initial FBR for pyrolysis and a second FBR for catalytic vapor-phase
upgrading, the focus of this paper is on the first reactor (pyrolyzer) .
In this reactor, biomass particles and fluidizing gas are fed into a
bubbling fluidized bed of hot sand, and the wood is thermally
decomposed into gas, tar, and char products, which exit from the top
of the reactor. Figure 1 provides general information about the reactor
geometry and typical operating conditions. More information about
the reactor system is available in the online documentation at https://
ccpcode.github.io/docs-2fbr/ and the study by Howe et al.46
In the experiments of interest here, the biomass under study was
pine wood that was initially pelletized and then crushed and sieved
through a 2 mm screen before being fed into the FBR. Each pyrolysis
experiment was run at a reactor temperature of 500 °C, with the wood
feed rate set at 1 kg/h for 2.5 h to achieve stable operation, so that
steady-state mass balances could be made. The initial sand charge
remained in the reactor throughout each experimental run.
2.2. Biomass Feedstock Properties. Statistical properties for the
external size and shape of the as-fed biomass particles and char
particles collected from the FBR experiments were optically
determined by MicroTrac using their PartAn3D analyzer, which
makes three-dimensional (3D) images of particle samples and
tabulates relevant parameters for up to hundreds of thousands of
particles.47 The data provided by MicroTrac was processed and
binned in MATLAB to summarize statistics that could be used to
DOI: 10.1021/acs.energyfuels.8b02309
Energy Fuels 2018, 32, 10683−10694
Energy & Fuels Article

Table 1. Key Input Parameters for Two-Fluid Reactor-Scale

Simulation in MFIX
property value unit
particle diameter (sand) 500 × 10−6 m
particle density (sand) 2500 kg/m3
particle density (wood) 500 kg/m3
particle density (char) 80 kg/m3
temperature 773 K
pressure (inlet) 133 kPa
fluidizing N2 (range) 0.249 m/s
minimum fluidization 0.0565 m/s
coefficient of restitution 0.9
angle of repose 55 deg
friction coefficient 0.1

Figure 1. (Left) Schematic illustration of geometry and operating
conditions of the 2 in. FBR system for thermochemical conversion of
biomass. As biomass particles are conveyed through the pyrolyzer and
elutriate from the top, they are converted into light gases, bio-oil, and
char to varying degrees depending upon their residence times. The
sand particles comprising the bulk of the fluidized bed are large and
dense enough to remain in the reactor. (Right) Example of the
conceptual control volume and boundary conditions described below
for use in the 2D axisymmetric single-particle simulations.
construct representative “nominal” particles in the particle-scale
simulations described below.
Internal microstructures of the biomass feed particles were
characterized with X-ray micro-computed tomography (CT) using a
ZEISS Versa 520 X-ray microscope (XRM) or X-ray computed
tomography (XCT) operating at 30 kV and 2 W (67 μA) using the
4× lens and no filter. This produced 3D CT images of the internal
structure with a voxel size of 3.4 μm, such as those depicted in Figure
5, by convolving the information from 1600 to 2400 two-dimensional
(2D) X-ray images as particle samples were rotated through 360°.
3. COMPUTATIONAL APPROACH AND
METHODOLOGY
3.1. Reactor Hydrodynamic Simulations. The global 3D
hydrodynamics of the NREL 2FBR pyrolyzer were simulated with
multiphase flow with interphase exchanges (MFIX),48 which is an
open source CFD package specifically developed for modeling
multiphase reacting flows. In this case, the specific objective was to
use the two-fluid approximation to estimate the residence times of
biomass and char particles. Values of the MFIX input parameters used
for these simulations are summarized in Table 1. The Sauter mean
diameters calculated from the 3D particle Feret lengths were 58, 278,
344, 426, and 543 × 10−4 cm. When simulations were run with a
density of 500 kg/m3, the fresh wood particles were found to have an
infinite residence time (they elutriated to the bottom of the reactor)
until they convert to char with a density of 80 kg/m3. Thus, running a
larger wood density would not change the effective particle residence
time, which was determined using eq 18, where Uwood is 0 and Uchar
was calculated to have a known value so that the results from initial
density of 500 kg/m3 were used.
The two-fluid approach approximates the gas and solid phases as
interpenetrating continua. The conservation equations solved for the
gas and solid phases for mass, momentum, and species in the fluid
domain are respectively given by
∂
(εgρg ) + ∇(εgρg ug) = 0
∂t (1)
∂
(εsρs ) + ∇(εsρs us) = 0
∂t (2)
∂
(εgρg ug ) + ∇(εgρg ug ug ) = ∇τg − εg∇Pg + εgρg g − β(ug − us, m)
∂
(3)
∂
(εs, mρs, m us, m) + ∇(εs, mρs, m us, mus, m)
∂t
= ∇τs, m − εs, m∇Pg + εs, mρs, m g − β(ug − us, m)
(4)
∂
(εgρg Xg, n) + ∇(εgρg Xg, nug ) = ∇Dg, n∇Xg, n
∂t (5)
∂
(εs, mρs, m Xs, m , n) + ∇(εs, mρs, m Xs, m , nus, m) = ∇Ds, m , n − ∇Xs, m , n
∂t
(6)
where g, s, s,m, g,n, and s,m,n describe gas, solid, solid-phase m, gas-
phase species n, and solid-phase m species n, respectively, ε is the
volume fraction, ρ is the density, u is the velocity vector, τ is the stress
tensor, P is the pressure, X is the mass fraction, D is the diffusion
coefficient, and β is the coefficient for the interphase force between
solid and gas phases. The gas−solid momentum transfer, in the
interphase force, used the Syamlal−O’Brien49 correlation for the drag
model. To model solid transport properties, such as solid pressure and
viscosity, the kinetic theory of granular flow,48 together with the
Schaeffer frictional stress tensor formulation50 and the sigmoidal
blending stress51 function, relates the computed solid temperature
with solid transport properties. Furthermore, the numerical simulation
used the species equation for tracking purposes, and there were no
chemical reactions. Separate mass inlet boundary conditions were
applied for the gas distributor and biomass inlet. A pressure outlet
boundary condition defined the outlet at the top of the reactor, and
wall boundary conditions were treated as no slip.
MFIX is capable of simulating extremely complex systems of
multiphase reacting flows. The specific conditions in the 2FBR
pyrolyzer make some important simplifications possible that reduce
the computational demand. Specifically, the 2FBR is operated such
that temperature gradients are minimized and the large excess of
diluent fluidizing gas relative to the biomass vapors makes it possible
to neglect volume changes in gas flow through the reactor.
Biomass and char residence time distributions and average
velocities in the reactor were determined in this study by seeding
the simulated biomass inflow stream with tracer particles having the
density of either raw biomass or devolatilized char. Runs were
completed using five different particle sizes (at a single fluidizing gas

10685 DOI: 10.1021/acs.energyfuels.8b02309

Energy Fuels 2018, 32, 10683−10694
Energy & Fuels Article

ij ∂u u yz
ρjjjj + (u∇) zzzz = −∇ρ
flow) to determine how the average particle residence times were
j ∂t εp z
k {
affected by the particle size. To estimate drag properties, the biomass

l
oji |
zyo
and char particles were treated as having spherical shapes

ojjμ(∇u + (∇u) ) − 3 μ(∇u)Izz}

+ ∇m o
corresponding to the Sauter mean diameter (d32) calculated from

nk {~
T 2
the Feret lengths from the MicroTrac particle analyses. The exit times
out of the top of the reactor were used to create biomass particle
residence time distribution (RTD) curves, which were then averaged (9)
to generate mean transit times. ∂ρ
To determine steady-state particle residence times, it was necessary + ∇(ρμ) = 0
to continue MFIX computations for ∼8 s beyond the initial startup to ∂t (10)
reach a condition where the statistics were stationary. Figure 2 shows The above differential balances can be restated as
∂T
(ρC P)eff = keff ∇(∇T ) − ρC P u∇T + Q
∂t (11)
∂ci
εp + ∇(− Di∇ci) + u∇ci = ∑ Ri (12)
∂t

ρ jijj ∂u u zy
jj + (u∇) zzzz = −∇p
j εp z
k {
l |
εp ∂t
o
o 1 ji o
+ ∇m j zyzo
}
o j
o εp k zo
o {o
o
2
n ~
T
μ(∇ u + (∇ u ) ) − μ(∇ u )I
3
ij y
ρ∇u zzz
− jjjjκij−1μ + zu
j εp2 zz
k { (13)
∂εpρ
+ ∇(ρ u) = ∑ Ri (14)
∂t
where ρ is the density, CP is the heat capacity at a constant pressure, T
is the temperature, k is the thermal conductivity, u is the velocity
vector, Q is the heat generation term, ci is the concentration of species
i, Di is the diffusion coefficient for species i, ∑Ri is the sum reaction
rates for species i, εp is the porosity, μ is the viscosity, I is the identity
matrix, κij is the permeability tensor, and the superscript T in eqs 9
and 13 denotes the transpose operator. The mass source term ∑Ri
represents the reactions from solid wood to vapor products
Figure 2. Reactor hydrodynamic simulation: cross-sectional image of throughout the porous medium. Radiation at the particle surface
char flowing through the FBR with sand. followed the Stefan−Boltzmann equation, with surface emissivity of
0.9 and ambient temperature of 500 °C. Heats of reaction (Table 2)
were applied through the volume of the particle. At the particle
surface, the boundary condition is simply equal flux, such that heat,
a cross section of the 3D reactor simulation for char flowing through mass, and species flux is the same on both sides. A fixed pressure
the fluidized bed with sand. On the basis of this result, total outlet boundary condition follows the equation:
simulation times of 20 s were used to generate statistics for which 2
transition effects could be eliminated.34 − p + μ(∇u + (∇u)T ) − μ(∇u) = − p0
3 (15)
3.2. Particle-Scale Pyrolysis Simulations. Our particle-scale
biomass pyrolysis simulations accounted for previously proposed The intraparticle generation and reaction of pyrolysis vapors were
reaction kinetics coupled to transient, intraparticle differential energy, simulated with finite element integration of the differential balances
species, and momentum balances for the particle characteristics assuming a relative gas flow traveling over each particle surrounded by
described above. Darcy’s law was used to describe the anisotropic a control volume, as illustrated in Figure 3. As explained below, the
fluid transport within porous biomass particles, in which porosity is kinetics used in this study included both “primary” reactions for the
represented as a continuum. The resulting differential balances are initial release of vapors from the solid phase and “secondary” gas-
summarized by phase reactions of the released vapors to create the final products. To
account for secondary vapor-phase reactions outside the particles with
∂T minimal computational effort, the released vapors were assumed to
ρC P = ∇(k∇T ) − ρC P u∇T + Q
∂t (7) have an average total residence time in the reactor based on the time
required for the fluidizing gas to transit from the middle of the bed
∂ci through the entire freeboard. This was determined to be about 1.4 s
+ ∇(− Di∇ci) + u∇ci = R i
∂t (8) from the fluidizing gas conditions used for the experiments of interest.

Table 2. First-Order Arrhenius Reaction Rate Parameters for Pyrolysis Reactions

1 (bio-oil) 2 (gas) 3 (char) 4 (secondary char) 5 (secondary gas) moisture desorption

Ai (s−1) 1.08 × 1010 11 4.38 × 109 11 3.75 × 106 11 1.0 × 105 52 4.28 × 106 53 5.13 × 106 54
Ei (kJ/mol) 14811 152.711 111.711 10853 10853 87.953
ΔH (kJ/kg) 25555 −2055 −2055 −4256 −4256 2700

10686 DOI: 10.1021/acs.energyfuels.8b02309

Energy Fuels 2018, 32, 10683−10694
Energy & Fuels Article

Figure 3. Illustration of the particle-scale modeling approach to account for both primary and secondary pyrolysis reactions.

Table 3. Parameters Used in the Single-Particle Simulations of Pine Pyrolysis

parameter description value reference
Cpwood heat capacity of the wood cell wall 0.1031 + 0.003867T kJ kg−1 K−1 59
Cpchar heat capacity of the char wall 1003.2 + 2.09(T − 273.15) J kg−1 K−1 58
Dbio‑oil diffusion coefficient of naphthalene at 500 °C 0.3 cm2 s−1 60
DN2 diffusion coefficient of nitrogen at 500 °C 1 cm2 s−1 60
ε0 porosity of wood 0.276
ksolid thermal conductivity of the cell wall 0.41 W m−1 K−1 57
kgas thermal conductivity of gas (steam at 500 °C) 0.067 W m−1 K−1
kH2O,L thermal conductivity of liquid water 0.61 W m−1 K−1
kH2O,V thermal conductivity of water vapor at 500 °C and 1.44 atm 0.067 W m−1 K−1
Kchar,axial axial permeability of char (5× wood) 1.17 × 10−10 m2 61
Kchar,radial radial permeability of char (5× wood) 6.67 × 10−15 m2 61
Kwood,axial axial permeability of wood, scaled by the porosity factor (εwood/0.65) 4.69 × 10−12 m2 62
Kwood,radial radial permeability of wood (Kwood,axial/17600) 2.67 × 10−16 m2 62
MC0 initial moisture content 1%
P0 average pressure above the reactor sand bed 109 kPa
Ti initial temperature of the particle at t = 0 298 K
Tr temperature of the reactor and carrier gas 773 K
ρwood density of the wood/char cell wall 1500 kg m−3

Integration of differential biomass particle balances is complicated
by the change in the properties of each particle as it transits through
the reactor and converts from a raw state to char, as illustrated in
Figure 1. The limiting average rise velocities and associated residence
times for particles of raw biomass and fully devolatilized char in the
depicted computational control volume (denoted U) were deter-
mined from the reactor-scale model for each particle size of wood and
char, as described above. As wood is converted to char, the effective
rise velocity increases as the particle density decreases. Thus, for
particle-scale simulations, Ui can be effectively estimated by scaling
between the limiting rise velocities for each particle size i based on
conversion (such that the smallest wood size was converted to the
smallest char size, etc.), as summarized by
Ui , t − (1 − α)Ui ,wood + αUi ,char
ρwood
α=1−
ρwood
0 wall (also for char in this study) is 0.41 W m−1 K−1.57 The heat
where ρwood is the density of partially converted biomass and ρwood0 is
the initial density of biomass before it reacts.
The varying average particle rise velocities can be related to the
average particle residence times in the reactor (tR) by numerically
integrating the particle velocity with respect to time until the particle
moves completely through the reactor to reach the exit at the top (Lt).
tR
Lt = ∫0 Ui , t dt
Thus, when the limiting particle rise velocities for raw biomass and
fully devolatilized char are available (e.g., from reactor CFD
simulations), it is possible to use the above relationship to relate
the average residence time of each particle to its average conversion at
the reactor exit.
The reaction rates used to track particle mass loss and complete the
differential particle balances used the Arrhenius kinetics developed by
Di Blasi,11,52 which track the conversion of pine wood into char and
lumped product classes of light gases and condensable vapors (often
referred to as “tar” or “bio-oil”). These kinetics also account for
secondary reactions, in which condensable vapors crack to light gases
and recondense to form additional char.53 Moisture desorption is
represented as an Arrhenius reaction for bound water.54 The
Arrhenius reaction rate parameters used in the present study are
provided in Table 2.
The initial water content in all of the simulations was assumed to
be 1% based on compositional analysis of the feedstock. The porosity,
permeability, and density were calculated at each time step and varied
with the conversion of wood into condensable vapors (bio-oil), light
(16) gas, and char. Other properties were held constant, including gas
viscosity, thermal conductivity of solid, and specific heat capacity. The
viscosity of the gas and any vapor was assumed to be 1 × 10−5 Pa s,
the viscosity of H2 at 300 °C. Thermal conductivity of the wood cell
(17)
capacity of wood was taken as [0.1031 + 0.003867T (K−1)] kJ kg−1
K−1.58
The value for gas permeability in non-pelletized wood was 11.2
darcy units in the longitudinal direction and 4.6 × 10−4 darcy units in
the radial/tangential direction.62 Permeability scales with a pore size
to the power of 2.63,64 For char, the permeability was taken as that for
wood multiplied by a factor of 5.61 The permeability was reduced by a
factor of 4 for the pelletized wood based on pore size analysis. The
(18)
permeability at a given time at a point in the particle is determined by
K wood, t ρwood Kchar, t (1 − ρwood )
Kt = +
ρwood ρwood (19)
0 0
where K is permeability, ρwood is the density of wood evolving with
conversion, and ρwood0 is the initial density of wood in the particle.

10687 DOI: 10.1021/acs.energyfuels.8b02309

Energy Fuels 2018, 32, 10683−10694
Energy & Fuels Article

Figure 4. (A) Biomass and char particle size distributions from the MicroTrac measurements. For convenience in the simulations described below,
these distributions were split into five bins spanning the sizes and shapes present in the feedstock. (B) Mean width and thickness of particles for
their respective particle ferret lengths used to construct single-particle representations.

Figure 5. X-ray computed tomographic data comparing the structure of (left) milled and (right) pelletized/crushed pine feedstock particles.

Additional key parameters used in the single-particle model are shown ε0(ρwood + ρchar )
in Table 3. ε=1−
ρwood (21)
The bulk diffusivity (Di) of bio-oil was taken to be the diffusivity of 0

naphthalene in nitrogen at 500 °C, and Di of gases and nitrogen was
taken to be the diffusivity of nitrogen at the same temperature.60
Inside the particle, the effective diffusivity Deff,i is based on the bulk
diffusivity and porosity65
ε (Dalton’s law):
Deff, i = Di
τ (20)
where ε is the porosity and τ is the tortuosity calculated by the
Millington and Quirk model66 to be ε−1/3. The initial porosities of
non-densified pine and poplar are 0.65 and 0.80, respectively, based
on the cell wall density of 1500 kg/m3 and reported bulk wood
densities.58 On the basis of the X-ray tomography data, the initial
porosity of our densified pine is 0.270. The porosity at a given time at
a point in the particle follows eq 21. The impact of the moisture
content on the porosity was ignored because the rate of pyrolysis
reactions is negligible below ∼350 °C
where ε is the porosity and ρchar is the density of char. The density of
the solid porous matrix was calculated by the following equation:
ρsolid = ρwood + ρchar + ρH O
0 2 L (22)
The density of vapor/gas was calculated by the following equation
p
ρgas = (Cgas + C tar + C N2 + C H2OV )
RT (23)
where R is the universal gas constant, p is the pressure, T is the
temperature, and Ci is the molar concentration of each species.
Reaction-coordinate-dependent shrinking was accounted for in the
reactor-scale model but not in the single-particle model because it has
been previously shown to have little impact at the particle scale.38
3.3. Canonical Ensemble Yield Calculations. As discussed
above, the as-fed biomass particles had a relatively wide range of sizes.
To account for this, five representative particle sizes were identified to
span the range of experimental sizes for reactor- and particle-scale

10688 DOI: 10.1021/acs.energyfuels.8b02309

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Energy & Fuels Article

simulations. Results for each size were then used to compute volume-
weighted averages for the expected bio-oil, gas, char, and unconverted
biomass yields predicted by the models that could be compared to
experimental measurements. This is summarized below, where y is the
yield of bio-oil, char, gas, secondary char, or biomass (wood), V is the
volume fraction, and i is the bin number.
i = 1:5
y= ∑ Vy
ii
bins (24)

4. RESULTS AND DISCUSSION

4.1. Experimental Feedstock Analysis. The as-fed
biomass particles have a relatively wide range of sizes, even
for the milled pellets, which have been screened to 2 mm prior
to feeding, as seen in Figure 4. It also appears that the char
particles exiting the reactor are typically much smaller than the
as-fed wood particles, with the most populous particle size
dropping from 2.3 to 0.4 mm in length. We speculate that the
harsh environment of the sand fluidized bed likely causes
significant attrition and fragmentation of the biomass particles
as they transit the reactor. Figure 6. Linear dependence of thermal conductivity upon specific
The XCT results provided porosity and pore structure as gravity.58
well as a basis for estimating the effective thermal conductivity
of the milled and pelletized biomass particles because the sizes of raw biomass and char particles were used to determine
thermal conductivity of woody biomass is linearly dependent the RTDs and mean reactor transit times for each particle class.
upon its specific gravity, which is dictated by the presence of Table 4 and Figure 7 summarize the results for both raw
void space resulting from the cellular tissue structure of
biomass.58 This dependence is illustrated in, for example, Table 4. Wood and Char Particle Residence Times for the
woody materials in Figure 5. Thus, we were able to estimate Five Representative Particle Sizesa
the original particle thermal conductivity from the XCT images
using the interior void fraction (denoted f v) that was revealed Feret length (mm) particle residence time (s)
by dividing the filled tomographic volume of the particle wood 0.76 2.67
interior by the total volume encapsulated by the exterior 1.52 -
particle boundary. Because the specific gravity of the cell wall is 2.27 -
largely constant at ∼1.5 among wood species,67 the total 3.03 -
density of the particle was estimated as ρ = (1 − f v)1.5 (g/ 4 -
cm3). The thermal conductivity was then estimated using the char 0.11 2.45
linear expression shown below the fitted line in Figure 6 by 0.44 3.31
generating a weighted average of the void space domain (kgas) 0.78 3.70
and the solid domain (ksolid) in the particles. 1.08 4.22
Another useful result from the XCT analyses is that the feed 1.44 4.69
a
preparation steps used in the experiments increased the Note that for all but the smallest wood particle size, the particle is
effective feed particle density from ∼540 kg/m3 for the milled predicted to not leave the reactor, as represented by “-”.
pine to ∼1096 kg/m3 for pelletized pine. This corresponds to
changes in the effective thermal conductivity from 0.12 to 0.23 biomass (pine wood) and char particles at various sizes based
W m−1 K−1 for the milled and pelletized feedstock, on the particle size distribution from the particle analyses
respectively. While it has been speculated that densification described above.
of biomass during pelletization can impact the particle As expected, the MFIX simulation predicted that larger and
microstructure and internal particle transport properties, this more dense particles had increased residence times in the
is the first time to our knowledge that the phenomenon has reactor. In cases where the as-fed biomass particles were
been experimentally verified. sufficiently large, it was not even possible to determine finite
Milling also appears to have an impact on the distribution of reactor residence times within the limits of the current MFIX
the biomass particle aspect ratio. Specifically, the milling simulations. This should not be surprising, because the physics
process used in the NREL experiments produces relatively of particle elutriation require that there is a critical size limit for
high-aspect particles that preserve the inherent directional biomass particles such that they are never able to elutriate from
microstructure. In contrast, XCT images of the pelletized feed the reactor unless the gas flow is increased. Conversely, the
particles appear to suggest more of a random agglomeration of smallest particles are almost able to attain the velocity of the
smaller particles, which has less net directional character. gas (near zero slip velocity), resulting in very short residence
4.2. Reactor-Scale Modeling. CFD modeling of the times nearly equivalent to the gas phase. The presence of such
2FBR with MFIX was used to estimate the residence times of critical limits illustrates the kind of strong nonlinear relation-
biomass and char particles to provide heating and reaction ships involved in selecting design and operating parameters,
time scales that could be applied to particle-scale pyrolysis such as particle size and gas flow, that need to be considered in
simulations. Specifically, the simulated behavior of selected optimizing pyrolysis FBRs.
10689 DOI: 10.1021/acs.energyfuels.8b02309
Energy Fuels 2018, 32, 10683−10694
Energy & Fuels
Figure 7. Superficial gas−particle slip velocity of gas around relevant
particle sizes (dashed lines) and average limiting particle rise velocity
through the FBR (solid lines).
4.3. Pyrolysis Yields from Coupled Reactor- and
Single-Particle-Scale Models. The particle-scale models
captured intraparticle heat conduction, mass diffusion, mass
convection, pressure, density, chemical reactions, and solid−
gas phase change. Particle-scale simulations were run for each
of the five representative pine particles over a range of reaction
times, to produce the conversion snapshots after 4 s, illustrated
in Figure 8. One notable observation revealed by these
simulations is that rather high velocities (up to 0.25 m/s) were
calculated for the pyrolysis vapors that were ejected from the
ends of the porous pine particle. The average particle
temperature and yields predicted by the particle-scale model
as a function of the exposure time in the reactor for different
size particles are summarized in Figure 9. The temperature
results illustrate that initial heating is very rapid for the smallest
particles (0.76 mm long), and they reach 95% of their final
temperature after only 0.7 s. However, the largest particles (3.8
mm long) take 4.9 s to achieve the same temperature, revealing
how dramatic the effect of feed particle size is on the heating
rate. This effect is due to a combination of the lower thermal
mass and higher surface area/volume ratio for the smaller
particles.
On the basis of the mean residence time predictions from
the reactor-scale simulations combined with the residence
time−conversion relationship represented by eq 18 and the
assumptions concerning secondary vapor-phase reactions
described above, the product yields at the reactor exit were
Figure 8. Predicted wood conversion and exit gas velocities for five different size particles after 4 s.
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estimated for these same particle sizes, as summarized in Table
5. Notably, the 0.76 mm particle, which has a residence time of
2.6 s, only achieves 87% conversion because its small size
makes it pass very quickly through the reactor before the
primary reactions can be completed. This also results in a
reduced predicted bio-oil yield of 49.6% by weight. On the
other hand, the 3.79 mm particle has a 9.3 s residence time,
allowing the primary reactions to be about 97% completed and
a higher predicted bio-oil yield of 55−56% by weight. Again,
these differences illustrate the importance of the particle size
on the pyrolysis performance. Of course, size effects should be
weighted by the relative abundance of each size. For example,
although the conversion of the 0.76 mm particles is relatively
high, these particles only account for about 1.1% of the
feedstock on a weight basis, and thus, they do not dramatically
affect the overall biomass conversion.
The predicted exit product yields from our simulations for
the 2FBR appear to agree well with the available experimental
values (within the estimated error limits), as also shown in
Table 5. This suggests to us that the basic computational
modeling approach that we have proposed for combining
computational simulations of reactor- and particle-scale
processes is sufficiently detailed to capture the major effects
associated with feed particle variations, without the addition of
arbitrarily fit parameters.
4.4. Additional Particle-Scale Simulations. To evaluate
the practical value of the particle-scale model implemented
here for process development, we also used it to explore the
predicted impact of changes in specific pyrolysis parameters.
Initially, we did this by considering the impact of changes in
the reactor temperature and particle residence time. Assuming
a single feed particle size of 2.27 mm and a constant gas
residence time of 1.4 s, the trends in the bio-oil yield and the
relationship between the reactor temperature and particle
residence time illustrated in Figure 10 were generated. These
results imply that there is an optimum combination of
temperature and particle residence time in pyrolysis reactors
that should produce the maximum bio-oil yield. In the specific
example depicted, this optimal bio-oil yield is predicted to
approach 69.5% by weight at a reactor temperature of 430 °C
(703 K). Such a yield is considerably higher than that achieved
to date in experiments with this FBR, indicating that significant
potential remains for additional process improvement.
As another example, we considered the joint impact of the
gas residence time and temperature changes on the bio-oil
yield, shown in Figure 11. The impact of the gas residence time
is enhanced as the temperature increases, particularly above
DOI: 10.1021/acs.energyfuels.8b02309
Energy Fuels 2018, 32, 10683−10694
Energy & Fuels Article

Figure 9. Yields (wt/wt from dry wood) of pyrolysis products from five selected particle sizes versus reaction time.

Table 5. Summary of Simulation Results Compared to Experimental Resultsa

bins volume-weighted average experimental yields
Feret length of wood (mm) 0.76 1.52 2.27 3.03 3.79
volume percent 1.1 34.3 50.7 12.0 1.9
Feret length of char (mm) 0.11 0.44 0.78 1.08 1.44
effective particle residence time (s) 2.6 5.4 6.6 7.9 9.3
gas residence time (s) 1.4 1.4 1.4 1.4 1.4
bio-oil yield 49.6 55.9 55.6 55.3 55.2 55.6 55.6 ± 1.3
char yield 7.85 9.3 9.77 10.1 10.5 9.2 11.3 ± 0.5
gas + water vapor yield 29.5 33.2 33.0 32.7 32.7 33.0 30.9 ± 1.7
wood conversion 87.2 97.6 97.3 97.0 97.1 97.2
a
Yields in wt/wt % from dry wood. Experimental error represents population standard deviation.

Figure 10. (Left) Effect of the particle residence time and temperature on the yield of bio-oil with varying particle residence times and (right)
optimal temperature versus particle residence time with a fixed 1.4 s gas residence time for the 2.27 mm particle.

560 °C (840 K), where the rate of secondary reactions is very decomposed to light gases in less than 0.1 s. Above this
high and over half of the initially generated bio-oil is temperature and with gas residence times greater than 2 s,
10691 DOI: 10.1021/acs.energyfuels.8b02309
Energy Fuels 2018, 32, 10683−10694
Energy & Fuels
Figure 11. (Left) Bio-oil yield and (right) gas yield with the temperature and gas residence time with a fixed particle residence time of 6.6 s for a
2.27 mm particle.
nearly all of the bio-oil is predicted to be converted into gas.
Interestingly, these results also suggest that there is a regime
with high bio-oil yields (greater than 50 wt/wt %) that is less
sensitive to the gas residence time between 400 and 450 °C
(673−723 K).
Clearly, these above examples illustrate the usefulness of
such particle-scale models for planning experiments, designing
reactors, and assessing the technoeconomic potential of
candidate processes. While the design and operating
limitations of the reference reactor considered in this study
may prohibit the realization of the predicted optimal
conditions, the computational simulations make it possible to
recognize important opportunities for future research.
5. CONCLUSION
The results reported here demonstrate that combined
implementation of separate reactor- and particle-scale models
can lead to new insights and opportunities for understanding
and improving biomass fast pyrolysis in fluidized beds. At the
reactor scale, it is feasible to simulate the biomass and char
particle residence times with sufficient accuracy using two-fluid
CFD at a reasonable cost in time and computing resources. At
the particle scale, it is feasible to integrate the differential
intraparticle heat, mass, and momentum balances with finite
element methods (FEMs) for selected classes of particles while
still including realistic assumptions about feedstock particle
size variations and microstructure. Taken together, the
combined information generated by independent simulations
with each of these models can be used to accurately predict the
experimentally observed product yields from the NREL 2 in.
fluidized bed pyrolyzer within measurement accuracy. As
additional kinetic details for the pyrolysis reactions of different
types of biomass become available, we expect that additional
experimental verifications for using this modeling approach will
be made.
For future work, we recommend continued utilization of this
type of multimodel simulation strategy for simulating multi-
scale biomass conversion processes. Combining information
generated by separate models that approximate the dominant
physics at different time and length scales would appear to
offer significant advantages in computational efficiency over
models that attempt to address all of the scales in detail
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simultaneously (e.g., such as CFD simulations that directly
couple hydrodynamics with chemical reactions37,38). For other
more complex process contexts, it may be necessary to account
more fully for multidirectional coupling among the scales
(rather than the one-way coupling implemented in this work),
but the potential advantages of making the information transfer
process more selective between separate, independently run
models would appear to be considerable.
■ AUTHOR INFORMATION
Corresponding Author
*Telephone: 1-303-384-7691. E-mail: peter.ciesielski@nrel.
gov.
ORCID
Gavin M. Wiggins: 0000-0002-4737-6596
Peter N. Ciesielski: 0000-0003-3360-9210
Funding
This work was authored by the 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 DE-AC36-08GO28308. Funding was provided
by the U.S. Department of Energy Office of Energy Efficiency
and Renewable Energy Bioenergy Technologies Office. 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.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors acknowledge Steve Deutch and Kellene Orton for
information and discussions about the FBR experimental
setup.
■
NOMENCLATURE
CFD = computational fluid dynamics
FBR = fluidized bed reactor
DOI: 10.1021/acs.energyfuels.8b02309
Energy Fuels 2018, 32, 10683−10694
Energy & Fuels
FEM = finite element method
MFIX = multiphase flow with interphase exchanges, a
reactor modeling software package
NREL = National Renewable Energy Laboratory
XCT = X-ray computed tomography
■
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10694 DOI: 10.1021/acs.energyfuels.8b02309

Energy Fuels 2018, 32, 10683−10694