pubs.acs.

org/EF Article

Scaleable Hydrotreating of HTL Biocrude to Produce Fuel

Blendstocks
Michael R. Thorson,*,$ Daniel M. Santosa,$ Richard T. Hallen, Igor Kutnyakov, Mariefel V. Olarte,
Matthew Flake, Gary Neuenschwander, Lisa Middleton-Smith, Alan H. Zacher, Todd R. Hart,
Andrew J. Schmidt, Teresa Lemmon, and Marie Swita

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ABSTRACT: Hydrothermal liquefaction (HTL) offers an attractive route

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to produce fuel blendstocks from wet wastes. Scaleable hydrotreating data

for the conversion of HTL biocrude to fuels is critical to the
commercialization of HTL. Herein, we simulate the pore diffusion of
hydrogen into the catalyst pores for the hydrotreating of HTL biocrudes
and conclude that standard hydrotreating catalysts will be pore diffusion
limited regarding hydrogen diffusion for HTL biocrude upgrading. By
changing the catalyst size (crushed vs extrudate catalysts), we confirm an
impact of pore diffusion on the overall hydrogenation rate of HTL
biocrudes. When using whole pill extrudates, likely with pore diffusion
limitations, we provide scale-able hydrotreating data for the stand-alone
hydrotreating of a HTL biocrude (derived from sewage sludge). By
running the reactor at two different hydrotreater scales (25x scale-up), we
confirm the data quality.

■ INTRODUCTION
Hydrothermal liquefaction (HTL) offers an economically
40 MJ/kg, a combined Oxygen and Nitrogen content around
10 wt %,17 and has also reported a significant content of sulfur.
attractive route to produce fuel blendstocks from wet-waste When fully hydrotreated, the HTL biocrude from sewage
pollutants such as sewage sludge, fats, oils, and grease (FOG), sludge gives an approximate diesel yield of 70% and a high
derived cetane number (DCN) of approximately 70.18 The
manure, and food waste. HTL converts wet wastes to a
projected minimum fuel selling price (MFSP) in the Pacific
biocrude oil by liquifying the solids in wet waste streams using
Northwest National Laboratory (PNNL) design case for fuels
a high-pressure, high-temperature tubular reactor with no
derived from HTL of wet wastes is below $3/gge by 2022 in
catalyst. The biocrude can be hydrotreated to produce fuel
some scenarios without credits such as Renewable Identi-
blendstocks.1−10 Further, sufficient quantities of wet wastes are
fication Numbers (RINs).19 The simple nature of HTL, the
available across the US to make a sizable dent in the
quality product, the similarity to petroleum counterparts, and
transportation fuel demand within the US. Specifically, 69
the attractive process economics have increased commercial
teragrams of wet-waste is generated annually in the United
interest in the technology.
States which could produce approximately 5.9 billion gallons of
HTL commercialization will necessitate economical and
naphtha (10−25% cut of the upgraded fuel) and diesel fuel
sustainable hydrotreating of the produced biocrude. In the
(70−85% of the upgraded fuel) per year through an HTL
2020 PNNL HTL design report, hydrotreating costs were
process.11,12
found to contribute to $1.72/gge of the projected 2022 costs.19
Hydrotreating is an effective means to remove oxygen in the
Because the cost of hydrotreating is such a significant fraction
form of water and nitrogen in the form of ammonia13 by using
of the overall HTL costs, the ensuring of scale-able data is
hydrogen in the presence of heterogeneous catalysts at
elevated temperature and pressure.14 The majority of hydro-
processing of HTL biocrudes in the literature focuses on stand- Received: March 29, 2021
alone hydrotreating with sulfided catalysts;14 however, other Revised: June 9, 2021
areas of development include coprocessing at refineries15 and Published: June 25, 2021
nonsulfided catalysts.16 When upgraded, HTL produces high-
quality fuel blendstocks. Typical HTL biocrude from wet
wastes has a high heating value (HHV) reported around 35−

© 2021 American Chemical Society https://doi.org/10.1021/acs.energyfuels.1c00956

11346 Energy Fuels 2021, 35, 11346−11352
Energy & Fuels pubs.acs.org/EF
paramount for an industrial engineer to accurately predict
commercial costs. To this end, high-quality kinetic data is
necessary to build reaction kinetics and reactor models to
predict hydrotreater performance at-scale.20,21
To be confident in hydrotreating costs and scalability, an
industrial engineer needs to ensure the laboratory data avoids
axial dispersion,20,22−25 wall effects,26 incomplete catalyst
wetting,27 and nonisothermal reactor gradients.28 Kinetic
quality data is critical to scale up a hydrotreating process
while achieving the anticipated yield, rate, and product quality;
maintaining operability; and limiting capital and investment
risk.
The data on HTL biocrude upgrading is limited in
comparison to the extensive data on the HTL process. Also,
recently published hydrotreating data used crushed catalysts
which can result in scale-up surprises due to pore diffusion
limitations not being accounted for.29,30 To limit scale-up risks
from laboratory data, we applied principles taken from
literature to enable the generation of kinetic data. Further,
whole extrudates are used to achieve scalable kinetic data from
a small lab-scale hydrotreater.
Pore diffusion limitations in catalysts can drastically
influence the hydrotreating activity and selectivity. Here, we
evaluate pore diffusion limitations for hydrogen in hydro-
genation catalysts using both simulations and experimental
results to understand the role of catalyst size on activity. On
the basis of our finding that the catalysts exhibit pore diffusion
limitations, we use whole pill extrudates to demonstrate a
scale-up from 4 g to over 100 g of catalyst with similar
performance in two different sized hydrotreaters using identical
whole pill catalysts in trickle-bed hydrotreaters.
■
EXPERIMENTAL METHODS
Reactor System. Two cocurrent, downflow, trickle bed, integral
hydrotreaters simulated the main bed of a hydrotreater system.31,32
Two high-pressure syringe pumps fed bio-oil into the inlet of the
reactor, and a MFC controlled the flow of high-pressure hydrogen. All
reactors were operated in integral, down-flow (trickle-bed) config-
urations. Whole-pill extrudates were copacked with an excess volume
of inert SiC fines (mesh 70) to dilute the catalyst as described by Al-
Dahhan.26 The catalyst was loaded in multiple zones to ensure even
distribution of catalyst throughout the length of the reactor bed. The
product was collected from chilled gas/collection separation contain-
ers. The liquid product was collected, the mass was recorded, and the
vapor products were quantified using an online gas chromatography,
enabling closure of the system mass balance. Specific reactor loadings
and WHSVs are provided with the results (Figure 1).
HTL Biocrude Feedstock. Hydrothermal liquefaction (HTL) was
used to convert biomass to a thermally stable biocrude, using hot,
pressurized water in the condensed phase, which was then
hydrotreated to a hydrocarbon fuel blendstock.19,33 Herein, we report
the hydrotreating of two HTL biocrudes: one derived from algae (to
study pore diffusion limitations) and one derived from sewage sludge
(to demonstrate a reactor scale-up) based on feedstock availability.
Both wet feedstocks were processed at PNNL in their engineering
scale Modular Hydrothermal Liquefaction System (MHTLS) system
at 350°C to produce the biocrudes used in this study.
In partnership with the Great Lakes Water Authority (GLWA), 30
5-gal buckets of primary sludge were collected from the Wastewater
Resource Recovery Facility (WRRF) in Detroit, MI and shipped to
PNNL using a dedicated custom critical shipment in a refrigerated
truck. The sludge was characterized and prepared as a 15−17 wt%
(total solids) pumpable slurry using an immersion mill. The slurry was
then processed at 12 L/h over 4 days (including startup and
shutdown) to produce approximately 25 kg of biocrude. For the test,
the MHTLS was configured in a pure plug flow configuration with
11347
Article
Figure 1. Schematic of the hydrotreater reactor.
most of the heating and cooling accomplished in a feed/product
crossflow heat exchanger. Separately, A 50:50 wood:algae blend was
processed at 12 L/h in a combined CSTR and plug flow
configuration.
Analytical Methods. Elemental components including carbon,
hydrogen, nitrogen (ASTM D5291/D5373), oxygen (ASTM
D5373mod), and sulfur (ASTM D1552/D4239), in addition to the
water content (Karl Fischer titration, ASTM D6869), were measured.
Viscosity and density measurements were conducted on a Stabinger
viscometer (Anton Paar SVM 3000) at 20°C. A modified ASTM
Standard Method D664 for determining the acid content of
petroleum products was used to determine both carboxylic acid
numbers and TAN (Total Acid Number) of biocrude. ASTM
Standard Method D2887 (Simulated Distillation Method) also was
used to analyze the hydrocarbon blend. Diesel cut samples were then
analyzed for derived cetane number (DCN) by ASTM D976. Cloud
point was measured according to ASTM D5772. Pour point was
measured according to ASTM D7346. Sulfur was measured by ICP-
AES (Inductively coupled plasma atomic emission spectroscopy).
■
RESULTS AND DISCUSSION
Pore Diffusion. If whole pill catalyst particles are not used
in all reactor scales and pore diffusion limits exist, the apparent
kinetics will be strongly influenced by catalyst size. Due to
pressure-drop limitations at industrial hydrotreater scales,
commercial reactors do not use finely crushed or powder
catalysts. To evaluate the propensity of HTL hydrotreating
catalysts to exhibit pore-diffusion limitations, mass transport
was simulated within catalyst pores for typical α-alumina
hydrotreating catalyst properties. The pore concentrations
within a typical catalyst were modeled using a publicly available
tool, Gradients.34 Hydrotreating catalyst properties were taken
from a typical NiMo hydrotreating catalyst on a α-alumina
support.34 Three catalyst geometries were simulated: (a)
catalyst extrudates (cylindrical) with a radius of 0.5 mm and a
length of 5 mm, (b) catalyst extrudates (cylindrical) with a
radius of 1 mm and a length of 5 mm, and (c) crushed catalyst
(spherical) with a radius of 0.05 mm. The catalyst properties
inputs were as follows: catalyst bulk density of 330 kg/m3,
catalyst thermal conductivity of 0.25 W/m/K, catalyst internal
surface area of 11m2/g, catalyst pore volume of 4.8 x 107 m3/g,
and catalyst pore tortuosity of 5.12,35
https://doi.org/10.1021/acs.energyfuels.1c00956
Energy Fuels 2021, 35, 11346−11352
Energy & Fuels
This evaluation simulated the concentration of hydrogen in
the pores assuming it was the limiting reactant. The solubility
of hydrogen was estimated to be 0.00145 g/g based on the
solubility of hydrogen in creosote oil at 400°C.36 The
properties of the crude oil was estimated based on the
properties of stearyl alcohol as follows: diffusion volume of 339
and molecular weight of 242 g/mol. The observed enthalpy of
reaction was estimated to be −40000 J/mol based on the heat
of reaction of hydrogenation of stearyl alcohol to octadecane.
The simulated concentration (hydrogen) profiles inside the
three simulated catalyst particles are shown in Figure 2. While
Figure 2. Simulated hydrogen concentration (mol/m3) within the
catalyst particles at the reactor inlet as a function of the particle center
(normalized to the radius) for three catalyst particles. Black, 0.1
spherical particles; red, extrudates with a radius 0.5 mm and a length
of 5 mm; and blue, extrudates with a radius 1.0 mm and a length of 5
mm. Dp is the catalyst diameter, and Lp is the length of the catalyst if
a cylinder/extrudate.
not simulated in this study, typical of a hydrogenation catalyst,
the temperature gradient across the catalyst was assumed to
have no meaningful impact on the overall reaction rate. The
simulated concentration gradient across the hydrotreating
extrudates under these conditions shows significant depletion
of hydrogen within the catalyst pores. The simulation is
Figure 3. Schematic of the reactor loading (not-to-scale) employed in configuration 1 (top) and configuration 2 (bottom). Configuration 2 used
whole extrudate catalyst particles diluted with inert fines in the main hydrotreating bed while configuration 1 used crushed (20−40 mesh)
extrudates in the main catalyst bed. Gray particles represent inert material, and black particles represent catalysts (extrudates or crushed).
pubs.acs.org/EF Article
intended to match the typical properties of a typical catalyst
which would be used to hydrotreat HTL biocrudes. The results
indicate that it is likely that the pore diffusion limitations play a
significant impact on the observed reaction rates for HTL
biocrude upgrading and that catalyst particle size will likely
impact the reaction rate. If crushed catalysts or whole pills are
used at a bench scale for HTL biocrude upgrading, a significant
impact may be observed when scaling up to the commercial
scale. It is recommended to use whole pills at all scales when
upgrading HTL biocrudes to obtain catalyst performance
under well controlled conditions (isothermal, plug flow, no
wall channeling) which will scale well to industrial conditions.
While smaller catalysts will improve the reaction rate,
pressure drop limitations will limit the catalyst particle size for
commercial embodiments. Typical commercial hydrotreating
catalysts have extrudate diameters of at least 1 mm due to
pressure drop and catalyst strength limitations in commercial
reactors.
To minimize scale-up surprises, it is important to use whole
pill catalysts as early as possible in the process development
process as discussed earlier.20 Thus, we employed the
industrially vetted approach of diluting the catalyst bed with
inert materials in a 24” long, 3/8” diameter reactor (SS
Swagelok tubing, 0.049” wall thickness) to eliminate catalyst
wetting, wall channeling, and dilution. The specifics of the
reactor loading are reported below.
Experimental Confirmation of the Role of Catalyst
Size on Reaction Rate. The above simulation indicated that
pore diffusion of hydrogen into the catalyst pores likely limits
the reaction rate of HTL biocrude hydrotreating. To confirm
the impact of particle size (or pore-diffusion) on reaction rate
when using commercial hydrotreating catalysts, two experi-
ments were run to confirm the impact of particle size on
hydrotreating performance. In both experiments, HTL
biocrude derived from a 1:1 chlorella algae:pine wood (silage
stored) blend was hydrotreated in the bench-scale hydrotreater
with a two-zone reactor. A two stage hydrotreater was used in
the described experiments with a CoMo hydrotreating catalyst
in the guard-bed (primarily to reduce the metals with some
heteroatom removal as well), followed by a NiMo catalyst in
the main-bed to provide deep hydrodeoxygenation (HDO),
hydrodesulfurization (HDS), and hydrodenitrogenation
(HDN). For both reactor scales, we confirmed isothermal
temperature profiles, plug flow, and wall channeling non-
idealities were sufficiently addressed to ensure quality kinetic
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Energy & Fuels
Figure 4. % oxygen(left), % nitrogen (left), and density (right) in the upgraded product as a function of reactor WHSV for the whole pills (open
points) and the crushed catalyst (filled points). The feed density, nitrogen, and oxygen were 1.049 g/mL, 2.98%, and 11.37%.
data by using a publicly available tool, Gradients.34 Both
reactor scales meet the basic requirements for good
isothermality, axial dispersion (mass and heat), as well as
minimal wall effects. Larger reactors more easily satisfy the
requirements of ideal contacting patterns compared to smaller
reactors due to the larger ratio of the reactor diameter to
catalyst effective diameter and the high superficial velocities
observed in commercial reactors (increased length).
To confirm the impact of particle size on hydrotreating
activity, two configurations were run. In configuration 1, the
guard bed (zone 1) consisted of a mix of CoMo catalysts as
extrudates: 10−20 mesh and 20−40 mesh in a ratio of
0.37:0.42:1.00. The guard bed was held at 325°C. The purpose
of the guard bed was to remove metals that have a high
propensity for plugging the reactor or depositing metals of the
catalyst surfaces, thereby deactivating the catalyst. While the
guard-bed provides mild heteroatom removal, the elevated
temperature of the main bed results in the majority of the
heteroatom removal taking place in the main bed. The main
bed (zone 2) consisted of crushed NiMo extrudates (20−40
mesh). The main bed was held at 400°C. The higher
temperature of the main bed resulted in significantly more
hydrotreating, including HDS, HDO, and HDN. In config-
uration 2, the guard bed (CoMo) used the same ratio of
extrudates: 10−20 mesh and 20−40 mesh catalyst, also at
325°C (the guard bed). However, the main bed (400°C) used
extrudates in place of the crushed catalyst (20−40 mesh). The
extrudates were diluted with an excessive amount of diluent
(SiC, 70 mesh), specifically 2g of SiC for every 1g of catalyst.
Figure 3 shows the packing of the reactor loading (not-to-
scale) employed in configuration 1 (top) and configuration 2
(bottom). Configuration 2 used whole extrudate catalyst
particles diluted with inert fines in the main hydrotreating bed,
while configuration 1 used crushed (20−40 mesh) extrudates
in the main catalyst bed. Gray particles represent inert material,
and black particles represent catalysts (extrudates or crushed).
The purpose of this configuration was to study the effect of
particle size on reaction rate. Following start-up, the reactor
was allowed to break-in for approximately 100 h before the first
sample was taken for analysis of the product properties
pubs.acs.org/EF Article
(density, nitrogen, and oxygen). In configuration 1 (crushed
catalyst in main hydrotreater bed), the reactor was sampled at
167 (WHSV of 0.41 hr−1), 276 (WHSV of 0.31 hr−1), and 288
h (WHSV of 0.85 hr−1). In configuration 2 (whole extrudate
catalyst in main hydrotreater bed), the reactor was sampled at
131 (WHSV of 0.41 hr−1), and 142 h (WHSV of 0.79 hr−1).
The upgraded products were analyzed for CHNOS and density
to compare the upgraded products (Figure 4). The measured
slope of the density at steady-state operation was 8.1 × 10−5 g/
cc/hr, giving us confidence that deactivation has a minor
impact on the steady state operation over the length of this
short experiment.
On the basis of the experimental observation that particle
size impacts reaction rate in addition to the predicted
concentration gradients, a subsequent scale-up study was
completed with whole extrudates at all scales to improve data
quality and reduce surprises with scale-up. A loading procedure
described by Al-Dahhan was used to copack inert materials in
the reactor in subsequent experiments.26 The use of whole
extrudates was critical to obtain scale-able data based on
apparent kinetics which incorporate both pore diffusion and
fundamental reaction kinetics.
Comparison of Hydrotreating Results in a Catalyst
Scale-Up by 25x. To confirm the data quality at the bench
scale with 4 g of catalyst, the reaction was scaled up to a
reactor using at least 25 times the amount of catalyst. If the
bench-scale reactor had additional pore diffusion or catalyst
wetting limitations, the larger scale hydrotreater would be
expected to have improved performance. Using whole pill
extrudates in both reactor scales helps reduce changes that
occur as a result of scale-up.
The following tests used HTL biocrude derived from the
GLWA material described earlier with biocrude mass and
carbon yields of 41% and 52%, respectively. The GLWA sludge
has a relatively high-fat content (27% fat on a dry ash-free
basis), which contributed to a high-quality biocrude with
relatively low density and viscosity.
The biocrude was then processed through a 2-step
hydrotreating process. First, the material was processed
through a hydrotreater guard bed at 325°C with a CoMo
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Energy & Fuels pubs.acs.org/EF Article

catalyst, as described above in a 400 cc hydrotreater. The

pretreated feedstock was further upgraded over a NiMo
catalyst at 400°C as described in the experimental section.
Figure 5 shows the density of the upgraded oil when using 4

Figure 6. Simulated distillation of the fully hydrotreated HTL

biocrude from the bench (red, filled diamonds) and engineering scale
(black, open squares).

Figure 5. HTL Biocrude density (filled, black squares) as well as

upgraded product from composite 1 at the bench scale (black open
circles) and engineering scale (filled, black diamonds), and upgraded
product from other composites in the engineering scale (filled, gray
diamonds).

and 111 g of catalyst in two scales of reactors. A variety of

alternative composites were tested in the 111 g reactor (gray
diamonds). The black diamonds indicate the same feedstock
composite in the larger, 400 cm3 hydrotreater as the feedstock
composite used in the small, bench reactor (open circles). The
density in the bench reactor at 47 to 56 h on-stream was
0.8161 g/cc as compared to 0.820 g/cc at 49 to 59 h-on-stream
in the larger, 400 cc hydrotreater. While the length of the
experiment was relatively short, the slight upward slope in the
density plot indicates there is some catalyst deactivation. The
deactivation from the bench-scale reactor (where only feed
composite was used) was 4.64 × 10−5 g/cc/hr when a
trendline was fit to the last six density measurements. Figure 6
shows good agreement between the simulated distillation of
the upgraded product from the two-scale hydrotreaters. Figure
7 contrasts the upgraded products from both reactors to that of
the HTL biocrude feed material.
Using whole pill extrudates in two reactor scales, we observe
similar upgraded fuel properties. The consistency of the data
from both scales is indicative of isothermal, plug flow with
good catalyst wetting, indicative of quality data for kinetic
development. This data can be used by an industrial engineer
to build fundamental reaction kinetics to guide commercial
reactor design and selection.
Diesel Cut Analysis. The upgraded fuel (83% mass yield)
from the engineering scale run produced a diesel-rich (71% in
the 240−380°C cut) fuel blendstock. The diesel pour point
and cloud point were measured at 6.0 and 5.1°C, respectively.
This can be tuned based on the diesel cut points and would
require isomerization as a stand-alone fuel in many locations.
The derived cetane was measured at 63.8. The HHV was
11350
Figure 7. Overlaid GCMS traces of the upgraded HTL biocrude in
the bench-scale (red) and engineering scale hydrotreaters as well as
the starting HTL biocrude.
measured at 46.84 MJ/kg. The sulfur was measured at 59 ppm
via ICP. The flashpoint was 55.0°C.
■ DISCUSSION
While the upgraded product makes a high-cetane fuel, several
scale-up considerations exist. The fatty acids in HTL biocrude
derived from sewage sludge result in an elevated total acid
number (TAN). HTL biocrude TAN typically falls between 40
and 110 mg KOH/g compared to traditional crude (TAN <
1.0 mg KOH/g).37 While the TAN is high, the corrosion of
fatty acids may be low, because the TAN is primarily from
weak carboxylic acids, rather than strong acids, such as HCl.
The higher nitrogen content of the biocrude can result in
additional NOx from the upgraded fuels, adversely affecting
fuel emission qualities, if not fully hydrotreated. Moreover,
nitrogen in the biocrude can react with acids to form gums and
a heavier fraction that phase separates inside the reactor
leading to operational issues.38
The metals loading of HTL biocrude is significantly higher
than the metal content in the distillate fraction which is fed to
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Energy Fuels 2021, 35, 11346−11352
Energy & Fuels
refinery hydrotreaters. High metal content will result in guard-
bed deactivation and/or plugging as the metal deposits in the
reactor and/or on the catalyst plugging the pores. This is
exacerbated in algae feedstocks that form metal−organic
complex porphyrins, which require higher reaction temper-
atures, and an active HDM catalyst such as NiMo to
hydrogenate the Fe-porphyrin complexes.30,33 Moreover, to
mitigate this, an engineer will likely need to employ catalysts
with larger pore volumes and lower surface areas, with active
Hydrodemetalizatoin (HDM) catalysts that can handle the
higher metal loadings of HTL biocrude, and also focus on the
removal of the metals through the use of guard-bed reactors.39
Thus, catalyst deactivation in both a guard bed and the fixed
bed reactor will be important to evaluate for process scale-up.30
The high cloud point and pour point of the diesel blendstock
are a result of the high C16 and C18 n-alkane content of the
fuel blendstock, which may lead to the blending limits of the
fuel and/or require isomerization for stand-alone applications.
Unlike pyrolysis oils, HTL biocrudes derived from wet
wastes do not suffer from more traditional oil stability such as
polymerization of the biocrude oil due to the extended time
the oil spends at 350°C in the HTL reactor or from low fuel
cetane due to the high fraction of n-alkanes in the hydrotreated
product. Important aspects for commercialization include
quantification of catalyst deactivation/regeneration, efficient
use of a guard-bed to protect the main hydrotreater bed, and
increase of the catalyst WHSV to be more in-line with
traditional diesel hydrotreaters (WHSV of 2 hr−1).
We have demonstrated that the catalyst particle size plays a
significant role in the scale-up of hydrotreatment of catalysts
for HTL biocrudes using both simulations and experimental
results. Using whole-pill extrudates in the reactor and by
copacking a reactor, we can produce scale-able kinetic results.
We were able to demonstrate a hydrotreated oil yield of 83 wt
% with a 4 wt % yield loss to lights (the oxygen in the biocrude
is converted to water via HDO: >95% via mass balance) when
hydrotreating HTL biocrude from sewage sludge. Also, the
acid number decreases to below the detection limit of the TAN
analysis, indicating that the heavier fatty-acids have trans-
formed into long-chain hydrocarbons. The hydrotreated oil
predominantly fractionates into a diesel blendstock as a high
cetane fuel.
■
CONCLUSIONS
We demonstrated that for the hydroprocessing of HTL
biocrudes, hydrogen diffusion into the catalyst pores can be
pore-diffusion limited, which impacts the apparent kinetics of
HTL biocrude using both simulations and experimental results.
By fixing pore diffusion limitations (using extrudates at all
scales) and addressing plug flow and temperature gradients
within two trickle-bed reactors, we are able to achieve scale-
able hydrotreatment data for HTL biocrudes, producing a high
cetane diesel with a large diesel cut (70%).
■
AUTHOR INFORMATION
Corresponding Author
Michael R. Thorson − Pacific Northwest National
Laboratory, Chemical and Biological Processes Development,
Richland, Washington 99352, United States; orcid.org/
0000-0002-1962-154X; Email: michael.thorson@pnnl.gov
pubs.acs.org/EF Article
Authors
Daniel M. Santosa − Pacific Northwest National Laboratory,
Chemical and Biological Processes Development, Richland,
Washington 99352, United States
Richard T. Hallen − Pacific Northwest National Laboratory,
Chemical and Biological Processes Development, Richland,
Washington 99352, United States
Igor Kutnyakov − Pacific Northwest National Laboratory,
Chemical and Biological Processes Development, Richland,
Washington 99352, United States
Mariefel V. Olarte − Pacific Northwest National Laboratory,
Chemical and Biological Processes Development, Richland,
Washington 99352, United States
Matthew Flake − Pacific Northwest National Laboratory,
Chemical and Biological Processes Development, Richland,
Washington 99352, United States
Gary Neuenschwander − Pacific Northwest National
Laboratory, Chemical and Biological Processes Development,
Richland, Washington 99352, United States
Lisa Middleton-Smith − Pacific Northwest National
Laboratory, Chemical and Biological Processes Development,
Richland, Washington 99352, United States
Alan H. Zacher − Pacific Northwest National Laboratory,
Chemical and Biological Processes Development, Richland,
Washington 99352, United States
Todd R. Hart − Pacific Northwest National Laboratory,
Chemical and Biological Processes Development, Richland,
Washington 99352, United States
Andrew J. Schmidt − Pacific Northwest National Laboratory,
Chemical and Biological Processes Development, Richland,
Washington 99352, United States
Teresa Lemmon − Pacific Northwest National Laboratory,
Chemical and Biological Processes Development, Richland,
Washington 99352, United States
Marie Swita − Pacific Northwest National Laboratory,
Chemical and Biological Processes Development, Richland,
Washington 99352, United States
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.energyfuels.1c00956
Author Contributions
$
These authors contributed equally
Author Contributions
The manuscript was written through contributions of all
authors. All authors have given approval to the final version of
the manuscript.
Funding
Pacific Northwest National Laboratory is operated for the U.S.
Department of Energy by Battelle under Contract DE-AC05−
76RL01830. Support is acknowledged from the U.S. Depart-
ment of Energy’s (DOE’s) Bioenergy Technologies Office
(BETO) of Energy Efficiency and Renewable Energy. The
views and opinions of the authors expressed herein do not
necessarily state or reflect those of the United States
Government or any agency thereof. Neither the United States
Government nor any agency thereof, nor any of their
employees, makes any warranty, expressed or implied, or
assumes any legal liability or responsibility for the accuracy,
completeness, or usefulness of any in-formation, apparatus,
product, or process disclosed, or represents that its use would
not infringe privately owned rights.
11351 https://doi.org/10.1021/acs.energyfuels.1c00956
Energy Fuels 2021, 35, 11346−11352
Energy & Fuels
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors thank the Great Lakes Water Authority (GLWA)
for providing wet waste feedstocks, including sewage sludge.
■
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Energy Fuels 2021, 35, 11346−11352