Biofuels Bioprod Bioref - 2021 - Fedie - Hydrothermal Catalysis of Waste Greases Into Green Gasoline Jet and Diesel

In the Field
Hydrothermal catalysis of waste

greases into green gasoline, jet,
and diesel biofuels in continuous flow
supercritical water
Ronald L. Fedie , Clayton V. McNeff, Charles V. McNeff, Larry C. McNeff, Peter G. Greuel,
Bingwen Yan, Julie A. Jenkins, SarTec Corporation, Anoka, MN, USA
Jason T. Brethorst, Grant B. Frost, Thomas R. Hoye, Department of Chemistry, University of
Minnesota, Minneapolis, MN, USA
Received November 06 2020; Revised November 08 2021; Accepted November 10 2021;

View online December 7, 2021 at Wiley Online Library (wileyonlinelibrary.com);
DOI: 10.1002/bbb.2322; Biofuels, Bioprod. Bioref. 16:349–369 (2022)
Abstract: The production of green gasoline, jet, and diesel biofuels from waste greases was achieved
using a novel hydrothermal, continuous-flow catalytic process operating under supercritical water
conditions, with recycled water the only added chemical. Thermally and chemically stable catalysts were
explored to optimize yields of liquid biofuels and to minimize production of gases and acidic compounds.
A 50:50 mixture of brown and yellow waste greases converted into 76.6 wt% liquid biocrude (BC); the
remainder converted to water and gases. Less than 0.2% of the feedstock (FS) formed carbon char
(mainly amongst catalyst particles). Various tubular reactors (Inconel, Hastelloy, titanium, stainless)
showed no interior defects, erosion, or mass loss after runs. The titanium catalyst was fully recovered
and regenerated back to its original potency. The BC was further refined into 28%, 48%, 20%, and
4 wt%, respectively for green gasoline, jet, diesel, and bunker. Biofuels were analyzed for compound
class compositions and reaction mechanisms were proposed. Hundreds of identified fuel products
(C3-C35) from processing oleic acid as a pure model compound were identified. The neat green gasoline
and diesel biofuels, along with a 50% green jet blend (with petroleum Jet A), were tested in appropriate
spark ignition, turbine, and diesel engines at the University of Minnesota Engine Labs. The biofuels
achieved 107.7%, 97.2%, and 101.3% engine power performance levels relative to petroleum fuels
(91-Octane, Jet A, #2 Diesel) along with lower CO and pollutant emissions. The biofuels complied with
American Society for Testing and Materials (ASTM) fuel specifications (D4814, D7566, D975) including
mandated corrosion and low sulfur limits of all three biofuels. © 2021 Society of Chemical Industry and
John Wiley & Sons, Ltd
Key words: hydrothermal; continuous; metal oxide catalysis; supercritical water; biofuels; green fuels;
renewable fuels
Correspondence to: Ronald L. Fedie, SarTec Corporation, 617 Pierce Street, Anoka, MN 55303, USA.
E-mail: ronfedie@sartec.com
© 2021 Society of Chemical Industry and John Wiley & Sons, Ltd 349
19321031, 2022, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/bbb.2322 by Koc University, Wiley Online Library on [10/05/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
RL Fedie et al. In the Field: Hydrothermal catalysis of waste greases into green gasoline, jet, and diesel biofuels
Introduction for the use of biofuels (to reduce greenhouse gas emissions) if
they are available.13 This alignment of strong market demand
I
deally, green biofuels are sustainable, better for the along with regulatory incentives creates a strong driving force
environment, and price competitive with fossil fuels, and for new developments in biofuel production.
they can be used within the existing petroleum-related There has been much interest in working with greener
infrastructure. To facilitate the transition from fossil fuels to solvents and the use of water is the ultimate green solvent.
renewable energy sources, the US Environmental Protection A recent review article focused on the essential aspects
Agency (EPA) enacted the Renewable Fuel Standard (RFS2), of subcritical and supercritical water (SCW) technology
which called for the use of a minimum of 28.0 billion gallons as applied to the extraction, hydrolysis, gasification, and
of renewable fuels in 2019, with increasing volumes in the carbonization of biomass.14 Various whole biomasses have
future.1 The Congressionally mandated RFS2 goal is to ‘use been studied with an eye towards optimizing reaction
at least 36 billion gallons of biomass-based transportation temperature, flow rates (SCW contact time), and the
fuels by 2022.’2 To put these numbers in perspective, annual percentage of biomass in the SCW. Conclusions drawn from
fuel consumption for the USA in 2019 was 142 billion these studies include that the subcritical and SCW water
gallons of gasoline, 47 billion gallons of diesel, and 18 hydrolysis processes need to be evaluated individually for each
billion gallons of jet fuel. Approximately 15 billion gallons raw material, and catalysis can improve process efficiency.
of distillate fuel, which could be used as diesel #2 fuel, was Continuous flow hydrothermal technology previously
also used as heating oil.3–5 In 2019, biofuel production in described by Elliot et al. also showed improvements compared
the USA was mostly 14.5 billion gallons of ethanol,6 but also to analogous batch process operation.15
2.6 billion gallons of biodiesel, 515 million gallons of green Recent studies of reactions in supercritical water have
(bio-based or renewable) diesel, and 3.9 million gallons focused on maximizing the product gases to produce syn-
of green (bio- or renewable) jet fuel produced based on gas directly from various biomasses efficiently,16 and much
RIN (renewable identification number) gallons.7 It should work has focused on studies with ligno- and hemi-cellulosic
be noted that there was roughly another 10% of imported feedstocks and supercritical water gasification (SCWG) to
biodiesel (266 million RINs).7 Surprisingly, there is no report specifically maximize hydrogen gas production.
of any commercially available ‘drop-in’ green gasoline being Three main active areas of study related to SCW biomass
produced, which ironically has the largest potential domestic conversion to renewable fuels are:
market. Significant improvement in developing new biofuel
1. The impact and influence of the process fluid
production technologies must be made to meet the goals
temperature on the kinetics of the degradation process
set forth in the EPA’s RFS2. Successful investments in new
and on the thermal stability of the products. Conversely,
domestic biofuel production technologies will contribute
the impact of pressure is generally observed to be less
to the US economy and increase national energy security.
significant than that of temperature.
Furthermore, the reduction of greenhouse gases and engine
2. The substrate-specific response to subcritical versus
emissions are important goals for the improvement of air
supercritical water conditions makes their development
quality in the USA.8 Fossil fuel use has well documented
and optimization dependent on feedstock (FS)
adverse effects on the environment because it releases
composition; thus, each different feedstock requires its
pollutants and sequestered carbon compounds into the
own study for optimization.
atmosphere.9 Biofuels recycle carbon through biomass capture
3. It is also necessary to understand the minimum
and have lower pollutant emissions, rendering them more
throughput of FS needed to ensure a sustained supply
environmentally friendly than fossil fuels.10 For these reasons,
chain relationship when attempting to scale up
a current market trend is to use biofuels to enhance the
subcritical/supercritical biomass processing schemes.
usefulness of petroleum products when a ‘drop-in’ equivalent
is commercially available. For example, recently a consortium Point 3 above raises perhaps the most significant factor
was formed ‘for the use and advancement of sustainable limiting the increase in production and use of biofuels in the
aviation fuels (SAFs), [which are] low-carbon and sustainably USA: the availability of inexpensive FSs that do not compete
produced alternatives to conventional, petroleum jet fuel.’11 with the food supply. As an example, over 75% of all biodiesel
Large companies that use aviation, like Federal Express and fuel currently produced in the USA is derived from food-
Southwest Airlines, have signed contracts for the use of biojet grade soybean oil (54%), corn oil (14%), and canola oil (8%).1
fuel; this is a continuing trend within the aviation industry.12 This makes biofuel production sensitive to FS cost, and the
Aviation customers have also expressed a strong preference practice of using highly refined food-grade oils makes FS
350 © 2021 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 16:349–369 (2022); DOI: 10.1002/bbb.2322
In the Field: Hydrothermal catalysis of waste greases into green gasoline, jet, and diesel biofuels RL Fedie et al.
pricing the predominate factor in the cost of production; the a mixture of mono-, di-, and triglycerides and free fatty acids
cost of FS represents >88% of biodiesel production cost.17 (FFAs). In one commercially available BG sample (Sanimax,
These production costs currently make the biodiesel industry Green Bay, WI, USA), the most abundant FFA was oleic
economically nonviable without government supports, tax acid (unsaturated C18 acid, 64%), followed by palmitic acid
incentives, mandates, or other subsidies. Lower cost, non- (saturated C16 acid, 20%), and stearic acid (saturated C18 acid,
food biomass sources would improve the economics of 9%), as shown in Fig. 1.
biofuel production and segregate it from the food industry.18 Despite the abundance of BG, it is well documented that
Alternatively, there is significant economic benefit from a vast amounts of waste BG have limited use commercially,
process that uses less costly inputs. For instance, current costs with most sent to landfills. These FSs have found little use
of raw materials are: soybean oil at $0.28/lb ($1.91 gal–1), due to (i) the elevated levels of free fatty acids (FFAs >70%),
yellow grease (YG) at $0.19/lb ($1.28 gal–1), and brown grease (ii) the relatively high sulfur content (100–1000 ppm), (iii)
(BG) (e.g., grease-trap waste,) at $0.07/lb ($0.47 gal–1), based the water content (10–20%), and (iv) the presence of other
on market prices as of January 2019.19 Hence, the price contaminants, each of which poses processing challenges when
difference between BG and food-grade soybean oil is more attempting to create bioproducts that meet American Society
than a factor of 4. To put this in perspective, heating oil diesel for Testing and Materials (ASTM) standards for biofuels. Two
is currently valued over $2 gal–1.20 The waste grease FS prices of the most common difficulties associated with using BG as
therefore show much more potential than food grade soybean a feedstock are undesired side reactions (e.g., glyceride ester
oil for processing into biofuels that could compete with saponification and production of additional FFAs)22 and sulfur
petroleum diesel fuel, depending, of course, on production poisoning of expensive catalysts sensitive to S-impurities.
and distribution costs. With an estimated cost for conversion In addition to the costs associated with precious metal
of $0.35 gal–1, there is a good economic opportunity to catalysts that cannot be reused, BG must also be separated
upgrade waste greases into biofuels. from product streams, neutralized, or treated as heavy-
In the USA, there is an abundance of BG in populous metal-containing waste streams. The relatively high sulfur
regions. The National Renewable Energy Lab (NREL) content typically found in BG makes it difficult to effectively
estimates that each person in the USA produces an annual use catalysis methods, which makes the conversion of these
average of 13 lb of trap grease and 22 lb of total grease.21 otherwise inexpensive feedstocks problematic.23,24 The main
Brown grease is found in grease traps and wastewater commercial process used for reducing sulfur levels in liquid
floatable fats, oils, and greases (FOGs). The NREL researchers fuels is hydrodesulfurization,25 a process commonly employed
studied domestic municipal wastewater21 treatment facilities in the petroleum industry. This process uses stoichiometric
and found an average BG content of 0.0035 wt%, concentrated amounts of hydrogen gas and requires the use of expensive,
as 5–20% of the floatable scum layer. As such, BG represents non-regenerable, or unrecoverable catalysts, thereby detracting
a substantial untapped potential feedstock material in the from the renewability of any technology that depends on this
USA with considerable potential for the production of process to reduce sulfur levels.25 Another impediment for the
sustainable biofuels on an industrial scale. The composition conversion of BG to biofuels is the presence of various impurity
of BG varies from source to source but it primarily comprises compounds that add to processing challenges: salts, dyes,
Figure 1. (a) A triglyceride present in brown grease (BG); (b) the hydrolyzed FFAs; and (c) a heated (50 °C), filtered BG sample.
© 2021 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 16:349–369 (2022); DOI: 10.1002/bbb.2322 351
herbicides, pesticides, and pharmaceutics, and by-products inexpensive, and both chemically and thermally stable, and it
from other municipal and common water-based processing: can be repeatedly regenerated to its original efficiency.
sewage, tanning, and paper processing, to name a few.
Despite its challenges, the conversion of BG into biodiesel Experimental
fuel has been reported previously.26 However, even using the
best current technologies, it has proven difficult and costly Materials
to process BG into biofuels that meet ASTM fuel-quality
specifications. Other researchers have used a variety of Porous monoclinic zirconia (size: 100 μm, pore: 300 Å), titania
pyrolysis techniques to convert BG into bio-oil mixtures,27 (size: 100 μm, pores: 80, 100, 300, and 500 Å), and alumina
but they also typically report that ca. 50% of the mass ends (size: 100 μm, pore: 300 Å) catalyst particles. A 500 g quantity of
up as solid char material and that high sulfur, FFA, and water each of the catalysts was obtained from ZirChrom Separations
levels remain in the pyrolysis oil, making them unusable as a (Anoka, MN, USA). Scanning electron micrographs (SEM)
replacement for petroleum-based liquid fuels. Alternatively, of the 100 μm sized catalyst particles are shown in Fig. 2, and
other groups have reported using enzymatic digestion to properties of the various catalysts used are shown in Table 1.
process BG, with one study demonstrating that fatty acid Water (high-performance liquid chromatography (HPLC)
decarboxylase in algae was the enzyme responsible for grade 18 mΩ), brown grease (Sanimax, DeForest, WI, USA),
converting FFAs into hydrocarbons (alkanes and alkenes).28 yellow grease (Cargill, Eddyville, IA, USA), and soybean oil
However, enzymatic processing requires precisely controlled (Costco, Coon Rapids, MN, USA) were obtained from the
conditions (T, concentration, pH, etc.) to achieve optimal indicated sources. The FS greases were heated to 50 °C, then
throughput rates and to keep fragile and expensive enzymes screened (80 μm) and filtered (5 μm) for pretreatment.
from denaturing; extra effort and expense are required to
separate the resulting complex product mixtures. Fixed-bed catalytic reactor
The novel process described here has been reported Cylindrical stainless-steel reactors with dimensions of 1.0 cm
previously,29 but here we describe the production of sufficient i.d. × 15.0 cm in length were fitted with 2 μm stainless steel
fractions of green gasoline, green jet, and green diesel fuel frits (Idex Corporation, Lake Forest, IL, USA) to seal the ends
to be used in engine and ASTM fuel test methods. This using stainless steel end fittings. The bottom frit was attached,
process offers the opportunity to use non-food, waste BG and the catalyst particles were dry-packed into the reactor
to produce renewable biofuels compatible with the present with vibration and tamping. The mass of the catalyst added
infrastructure. Moreover, these meet the petroleum ASTM was held constant in each run. The top end frit and cap were
fuel specifications, including low sulfur limits, for the installed, and each reactor was preconditioned by passing
synthesized green gasoline, jet, and diesel biofuels. The 100 mL of HPLC-grade water through it at 4000 psi back
hydrothermal catalytic process uses supercritical water as pressure in order to pressure pack the catalyst bed (chosen
the reaction medium, which after cooling naturally separates catalysts retained their catalytic viability throughout the
from the BC products and can be recycled back through the ongoing high pressure and temperature condition flow runs
system in perpetuity. The porous catalyst is fully recoverable, until coking).
Figure 2. Scanning electron micrograph of 100 μm, 300 Å pore size: (a) zirconia, (b) alumina, and (c) titania.
Table 1. The catalyst particles used to process the waste grease biomass and their physical properties.
Catalyst (type) Average size *cost (per gram) Average pore Surface area Apparent Crystal form
(μm) size (Å) (m2/g) density (g/cm3) (pure)
Zirconia 100 μm $4.00 300 30 2.6 Monoclinic
Titania 100 μm $0.95 80 85 1.4 Anatase
Alumina 100 μm $0.01 300 108 0.98 Part α-Al2O3
*Vendor: Zirchrom Separations Inc. (Anoka, MN, USA).
Figure 3. Flow diagram for catalytic hydroprocessing of BG feedstocks into biocrude (within seconds) then distilled into (1)
green gasoline, (2) green jet, and (3) green diesel biofuels.
Continuous biofuels production system each placed on a balance and masses were taken at periodic
design intervals to determine accurate flow rates and mass balance.
Gas product samples were collected into 20 mL glass vials with
The full catalytic flow system description and liquid and
gas line needles through sealed septa allowing the gas to flow
gas product collection procedures have been previously
through for several minutes before sealing off for analysis. A
described, along with a diagram (provided in the SI for
reactor load of catalyst processed 1.5-2 L of FS material before
convenient access) of the system apparatus components.29
becoming coked and beginning to plug, noted by a 300 psi
increase in system pressure. The processed product liquid
Experimental procedure was collected and allowed to separate into biocrude oil (top)
The reactor, assembled with the selected metal oxide catalyst, and water (bottom) layers. The resulting BC layer was then
was connected vertically into the flow line and positioned collected and distilled at ambient pressure into green gasoline
within the thermal oven. To preheat the reactor to the desired (bp 40–65 °C), jet (bp 65–130 °C), and diesel (bp 130–220 °C)
temperature, water was run through the system while adding fractions with the liquid distillation remains going to green
heat and maintaining the system back pressure. Once the bunker fuel. Typical glass distillation apparatus was used:
system was at the target temperature of 550 °C, the water flow heater, 5 L pot, Vigreux column (44 cm), water-cooled
rate was adjusted to 12.00 mL min–1 and the waste grease was condenser, and collection flask (ice-cooled for the gasoline
then simultaneously introduced at 8.00 mL min–1. This 2:3, fraction). A 3 L charge of BC was distilled over a 12–14 h
FS:water volume flow ratio was maintained throughout the period. A general process diagram to go from the waste grease
studies. After steady state was achieved in terms of flow rate, FS to the green fuels is shown in Fig. 3. The stainless steel (SS)
temperature, and pressure, the inlet water and FS flasks were reactor had the same mass after extended use along with its
same smooth-walled interior, and thus demonstrated no signs reactor under continuous flow conditions in supercritical
of corrosion throughout the processing of this high-acid FS water (SCW). Alumina catalyst is known not to be chemically
with the SCW conditions. The only difference in the SS was stable while heating to SCW conditions (temperature > ca.
a ‘gun-blue’ color (from its original shiny, metallic color), a 375 °C) and this was also observed as the reactor plugged
process well known to gunsmiths who purposely expose SS to while flowing and heating water alone with alumina.
high temperature to obtain the desired bluing. Zirconia and titania metal oxide catalysts therefore became
the focus of further work because they were observed to be
Instrumental analysis and engine testing completely stable under SCW conditions (high pressures and
temperatures) over extended use. Table 1 shows some costs
The biofuel products produced in this work were studied with
and physical properties of the catalysts used in this study.
the same spectroscopic techniques as described previously,29
The initial head-to-head comparisons were conducted using
mainly using gas chromatography–mass spectrometry (GCMS),
100 μm particle size catalysts (Fig. 2), all with 300 Å average
proton nuclear magnetic resonance (1H-NMR), and Fourier-
pore size.
transform infrared (FTIR) analyses. Gas products were analyzed
with headspace gas chromatography–mass spectrometry
(HS-GCMS) and gas-phase FTIR spectroscopy. Green fuel Reaction process runs to optimize
liquid samples were sent to the University of Minnesota temperature, pressure, and catalyst ratios
(1–1.5 gal) to measure their engine fuel power performance and for conversion of 50:50 (BG:YG) into
engine exhaust emission values, and to commercial laboratories biofuels
(0.5 gal) for the ASTM petroleum fuel specification tests.
The compositions of the resulting biocrude produced at
various temperatures using the zirconia and titania catalysts
Results and discussion was analyzed by GCMS and are shown in Fig. 4. Interestingly,
the two catalysts produced biocrude products with similar
Investigation of different metal oxide chemical compositions. Zirconia gave a larger fraction of
catalysts higher molecular weight ketones at a lower temperature
Initial research focused on testing the use of three porous (e.g., compare chromatograms at 450 °C in the 40 - 50 min.
catalysts: alumina, zirconia, and titania, in the fixed bed R.T. range), but in general the two chemical compositions
Figure 4. Gas chromatography–mass spectrometry chromatograms of the biocrude produced using 100 μm, 300 Å pore size
(a) titania catalyst and (b) zirconia catalyst (see Table 1) at different reactor temperatures while holding the pressure constant
at 3300 psi and flow rates of 2 mL/min FS, 6 mL/min water.
were remarkably similar, suggesting that similar mechanisms

are operative with each of the two catalysts. The effect of
temperature on the reaction outcome was also similar for
both catalysts. Temperatures of 570 and 590 °C resulted in
higher gas evolution of 33% and 41% by mass, respectively,
so a reactor temperature of 550 °C was determined to be an
optimum between biocrude quality and highest conversion
to biocrude liquid (with correspondingly lower conversion to
gases).
Because of its stability advantages over alumina and
significant cost advantages over zirconia, titania was the focus
of the remaining optimization studies and was studied with
a wide range of surface area and pore-size catalysts (Table 1).
The addition of acid catalysts, acetic and formic acids, to
the FS mixtures (with the metal oxide catalysts) showed no
Figure 5. Gas chromatography–mass spectrometry
discernible differences in the output biocrude products, except
chromatograms of the biocrude resulting from the FS
for undesirable greater gas mass output and acetone in the
processed under the same conditions (T, P, and flow rates)
biocrude (acetone is the ‘dimer ketone’ product of acetic acid). with different pore size titania catalyst.
Reaction process runs to optimize

catalyst contact time, catalyst pore size,
and pressure for conversion of 50:50
(BG:YG) into biofuels
A 50:50 (BG:YG) mixed grease FS was used to maintain the
input mixture in a lower viscosity fluid state at 50 °C. This was
important to keep the lipids from gelling in the stainless steel
HPLC pump heads and allow the FS to be delivered at high
pressure into the continuous flow reactor system efficiently.
Flow rates were varied to give 20 to 120 s catalyst bed contact
times of the FS:water (2:3, vol:vol) mixture. Variations
in contact times (flow rates) and temperature had highly
correlated effects on the resulting biocrude. For example,
the 60 s contact time at 500 °C resulted in a highly similar Figure 6. Gas chromatography–mass spectrometry
composition of the biocrude from a 45 s contact time at chromatograms of the FS processed with titania at 550 °C
525 °C using the same catalyst and FS:H2O input. The effect of and flow system pressures ranging from 2000 to 5000 psi.
biocrude product output with different process temperatures
is shown in Fig. 4. On a flow volume basis, the ratio of The final optimization study focused on the variation of
FS:water remained constant at 2:3 for the optimization studies. system pressure at a fixed temperature of 550 °C using the
To test the effect of surface area of the catalyst on the output 100 μm, 80 Å pore titania catalyst (Fig. 6). We determined
biofuel product, different titania catalyst average pore sizes that higher pressures slightly increased the yield of
ranging from 80 to 500 Å were examined. A comparison of lower molecular weight compounds (green gasoline
the GCMS data from the output biodiesel products is shown fraction) with a corresponding decrease in the amounts
in Fig. 5. The smaller pore catalysts have higher surface area of higher molecular weight compounds in the resulting
per unit mass and were expected to be more catalytic, with biocrude (data not shown). Thus, we determined that
more possible contact sites, and this was supported by the it was important to maintain a system pressure greater
results. The general trend observed was that the smaller pore, than SCW (>3205 psi) to obtain the highest percentage of
higher surface-area catalyst was more reactive and resulted liquid biofuel fractions. However, higher pressures also
in reduced formation of undesirable higher molecular weight resulted in a greater FS mass portion converted to gaseous
ketones in the biocrude product. products (primarily methane, ethylene, ethane, propylene,
propane, and butylene). A pressure of 3300 psi was Mass balance of 16.8 kg of BG processed
therefore used in all the remaining studies to minimize under the optimized conditions
the amount of higher boiling point (higher MW)
To test the properties of the target biofuel fractions
compounds produced without excessively increasing
using ASTM methods and in engine combustion trials, a
the percentage of FS converted into less desirable gas
production run was undertaken to generate the requisite
products.
amounts of the three biofuel fractions: green gasoline, jet,
and diesel. For this study, over 15 kg of BG was processed
Regeneration and reuse of the reaction
with the titania catalyst at 550 °C and 3300 psi in serial
catalyst
batches over several weeks. The mass percentage of the
To demonstrate that the titania catalyst could be liquid biocrude product (relative to FS mass used) over the
regenerated, it was removed from the reactor after it was series of production runs (samples analyzed every 1 or 2 L)
coked from use in producing biocrude and heated in a is shown in Fig. 8. In general, the FS conversion remained
stream of oxygen at 400 °C for 3 h, as previously described.29 consistent over the entire run, with no significant difference
The resulting material was re-evaluated for catalytic activity. in chromatographic analyses or liquid mass production rate
Figure 7 shows that the resulting GCMS chromatogram of of the biocrude products over the 10 weeks of 13-catalyst
the biocrude produced with the reactivated catalyst was bed changes and runs. In summary, the percentage
nearly identical to that from fresh titania. Figure 7 also biocrude liquid produced over the production run averaged
shows pictures of the fresh, coked, and regenerated catalyst 76.2% ± 2.0% over 21 L (16.8 kg) of FS processed.
where the regeneration restored the catalyst to its original The rest of the mass of FS was converted into a mixture of
color and the catalyst mass was found to be completely combustible gaseous products and water. From HS-GCMS
recoverable after thermal treatment (14.4 ± 0.1 g fresh and and gas-phase FTIR analysis, the gaseous mixture comprised:
after regeneration), hence there is no discernable difference 2.6% N2, 2.8% CO, 1.5% CH4, 17.7% CO2, 7.0% C2H4
in the catalyst from before and after thermal regeneration. (ethylene), 10.5% C2H6 (ethane), 7.1% H2O, 24.7% C3H6
After the regenerated catalyst was used/carbonized, it (propene), 16.2% C3H8 (propane), and 9.9% C4H8 (butene).
was regenerated and used a third time to process, and It is notable that nearly half of the gas mixture consisted
again showed the similar array of BC products. This is an of C2-C4 alkenes. An additional 0.4% of the FS mass was
important attribute from an economic standpoint, that the converted into larger gaseous compounds (≤ C5) that were
titania catalyst can be readily recovered, regenerated, and condensed as liquids in an ice-cooled gas outlet cold trap, and
reused repeatedly with the loss of only minute amounts this was added to the BC liquid mixture, for a final average
during transfers (a few grains, <0.1%). A full analysis of the of 76.6% FS (w/w) conversion into the liquid BC product.
regenerated catalyst, including an SEM and BET isotherm, Some gas products may come from the further processing of
is planned for future studies. glycerol that resulted from the glycerides in the FS.
Figure 7. Comparison of fresh and regenerated catalyst.

Chromatograms of the biocrude product run with fresh (a)
and thermally regenerated (c) titania. Images of fresh (b) and
thermally regenerated (d) titania. For comparison, an image Figure 8. The wt% of biocrude produced under optimized
of coked catalyst, prior to regeneration, is also shown (e). conditions over long-term, multi-batch processing.
Distillation of the biocrude liquid into fuel

fractions
Three liter volume portions of biocrude were subjected to
fractional distillation runs. After collecting the first fractions
(green gasoline) without any vacuum applied, a vacuum
of 5 Torr was used, which allowed the green jet and green
diesel fuel fractions to be distilled at lower temperatures.
Appropriate distillation fractions (with similar boiling point
ranges) were combined to create the green biofuels with
GCMS chromatogram arrays comparable to those of the
respective petroleum fuels shown in Fig. 9. The masses of the
distillation fractions that were combined to create the biofuels
gave average mass percentages of 28% green gasoline, 48%
green jet, and 20% green diesel from the distilled BC. The
remaining 4% viscous liquid distillation residue could be put
to good use as green bunker (marine) fuel.
Compound class composition of biofuel

fractions compared to petroleum fuels
The overall compositional analysis separated by chemical
functional group for the green biofuels and petroleum
fuels are shown in Fig. 10. Some differences were observed
Figure 9. Gas chromatography–mass spectrometry between the green biofuels (FAA-mandated 50/50 jet fuel
chromatogram comparisons for (a) green diesel vs. #2 diesel; blend maximum) and their pure petroleum counterparts in
(b) green jet vs jet A; (c) green gasoline vs 91-octane gasoline. relation to their percentages of alkane, alkene, aromatic, and
Figure 10. The percentage of compounds of various functional group classes present in petroleum standard fuels compared
to 100% green gasoline, 100% green diesel, and 50% green jet (blended with 50% jet A) fuels.
minor ketone functional groups. The ketone concentration desired reaction pathways over undesired ones and can often
was found to be dependent upon the temperature, contact improve reaction selectivity and yields. In the present case,
time, and catalyst surface area. These compounds could this understanding could, for example, allow for processing
mostly be eliminated at elevated temperature or by using of FS into more liquid fuel than gaseous compounds or for
longer catalyst contact times. In general, higher temperature, producing larger quantities of higher-value fuel fractions
higher surface area, and longer catalyst contact time also (e.g., green jet) over lower-value fractions (e.g., green diesel).
resulted in higher gas evolution. It has also been suggested However, gaining direct mechanistic insight into a process
that a final hydrogenation step could be undertaken to as complicated as the conversion of a multicomponent waste
remove all non-paraffinic groups. FS (such as BG) into fuel compounds is inherently complex.
One of the most abundant aromatic hydrocarbons To address this challenge, we studied the behavior of selected
produced was toluene, which is found at over 10% model compounds that are representative of some of the
concentration (GCMS peak area percentage) in the first predominant functionalities (acid, ester, ketone, alkane,
green gasoline fraction. Additional aromatic hydrocarbons alkene, and thiol) present in BG, listed in Table 2.
with higher molecular weights and boiling points appeared Here we summarize some of the observations using the
in higher boiling fractions. The xylenes and ethylbenzene pure model compounds (MC) as feeds into the reactor at 1:3
composed another 9% of the green gasoline fraction. Overall, and 1:6 (vol:vol, MC:water) ratios. A future communication
toluene, xylenes, and ethylbenzene compounds accounted is anticipated to report additional analysis of these sorts of
for >75% of the aromatics in the green gasoline fraction, processes. We analyzed the array of products formed when
not unlike petroleum fuels. These aromatic compounds each of these was passed/processed through the titania
assist with obtaining higher octane values in gasoline fuels catalyst and SCW reactor.
versus linear paraffins.30 They are also important in jet and Various processing conditions (temperatures of 350–550 °C
diesel fuels for lowering the freezing point and keeping the and pressures ≥3205 psi) were studied. The contact time
fuel from gelling. One reason biomass may be challenged to (liquid volume flow) in the reactor was held constant
produce valid jet fuel is that biomass processed into biojet (1 min). The properties of water change dramatically as it
typically has had little to no aromatic content.31 transcends from ambient conditions to the supercritical
phase (Tc = 374 °C and pc = 3205 psi).32,33 Of particular
Mechanistic considerations of model note, the dielectric constant (ε, relative permittivity), a
compounds measure of solvent polarity, plummets from 78 to 6. The
unique properties of SCW permit reactivity that is typically
Understanding the mechanism by which a chemical
inaccessible in other solvents or media. These studies helped
transformation takes place is important for promoting
identify several processes pertinent to the conversion of BG
into biofuels. A few relevant to the production of BC material
Table 2. The pure model compounds individually by these SCW/titania conditions are shown in Fig. 11: (i)
processed in phase I. ketonization of FFAs to produce ‘ketone dimers’;34 (ii)
Octanoic and Octane Methyl octanoate thermal fragmentation of aliphatic chains including those
stearic acids within ketones35 (see more fragmentation details in Fig. 12);
Oleic acid Hexadecane Glyceryl trioctanoate
and (iii) desulfurization of thiols.36 Cyclization to aromatics
2-octanone 1-octadecene Octanethiol (with unsaturated FFAs, glycerol, early products, Diels–Alder
Figure 11. Reactions of importance for the conversion of waste grease feedstock into fuel compounds.
Figure 12. Important events in the homolytic thermal cracking of aliphatic ketones to smaller ketones and hydrocarbons.
Figure 13. Main steps in the titania-catalyzed carboxylic acid ketonization mechanism.
reactions, ketone condensation, etc.) could also be occurring, Processing pure oleic acid as a model
and these are being considered in ongoing studies. compound
Titania is known to promote the ketonization of free fatty
acids.37 This transformation is valuable for fuel production Oleic acid (C18H34O2) was studied as a model compound
because it simultaneously accomplishes two important with a 1:6 (H2O:oleic acid) volume flow ratio at a temperature
things: (i) it reduces the levels of acidic functional groups, of 550 °C and pressure of 3300 psi using a 30 s catalyst contact
thereby diminishing the corrosive properties of the resulting time. This produced a mixture of products in the liquid
biofuels, and (ii) it rapidly decreases overall oxygen content, BC, which separated on top of the water phase and had a
through the loss of CO2 and H2O, without requiring a similar appearance as the top-phase liquid BC product from
stoichiometric reductant (e.g., H2) that is common to other processing the brown and yellow greases (see Fig. 3). The
refining technologies. The use of high-valent metal oxides GCMS chromatogram of the resulting BC product layer from
such as titania as a heterogeneous catalyst to promote this processed oleic acid was collected and is shown in Fig. 14.
reaction in the gas phase has received considerable attention, Analysis, aided by the MS library, led to the identification
including mechanistic investigations.38,39 The essential of 226 product compounds in the BC mixture. These are
aspects of this ketonization reaction are shown in Fig. 1. listed in Tables 3–5 according to increasing retention times
An important role of titania is to facilitate enolization of a (tR) along with their peak area percentages and quality hit
surface-bound FFA. This allows a second surface-bound values from the library (also listed as percentages). There
FFA to undergo a Claisen-like condensation reaction to are compounds in addition to the ones listed in these tables,
form a β-ketoacid with release of a molecule of water. but these had less than 0.010% peak area and/or received
Decarboxylation of the resulting β-ketoacid provides, low quality library matches of <50%, with a 99% match
initially, an enol (not shown) that quickly tautomerizes the highest possible. The GCMS analysis of the BC liquid
to the ketone product. Due to its low binding affinity, from oleic acid showed various carbon-number-containing
the ketone dissociates from the metal oxide surface. compounds from C3 (propene, tR = 1.21 min.) up to C35
Interestingly, we can find only three reports of metal oxide- (tR = 42.38). This C35 compound was identified as the ‘dimer
catalyzed ketonization in SCW; however, each offers only ketone’ of the C18 acid molecule (i.e., 18-pentatriacontanone).
limited mechanistic insight.37,40,41 The symmetric dimer ketone is well known to be produced
Figure 14. Gas chromatography–mass spectrometry chromatogram of the biocrude products from processed oleic acid.
from carboxylic acids, including a good percentage of and 1-octadecene, which suggested that homolytic thermal
8-pentadecanone (C15) produced when pure octanoic cracking mechanisms (see Fig. 12), analogous to those
acid (C8) was the model compound feedstock. So, quite encountered in petroleum refining, are operative in SCW
interestingly, the process produces many larger compounds at these high temperatures.42 Aliphatic ketones degraded
with a higher number of carbon atoms than the parent more quickly (at lower temperatures and more completely)
compound processed. than the pure hydrocarbons, presumably because the rate of
The BC liquid products from the mixed waste greases the homolytic initiation step is greater for the weaker OC–
covered the carbon-containing range from C3 to C35. This CH2CH2R (α-homolysis) and OCCH2–CH2R (β-homolysis)
variety of hydrocarbons is also found in petroleum crude bonds near the carbonyl group. There is evidence in the
mixtures (Cn hydrocarbons with nearly any n value, and literature that SCW may be an ideal medium for thermal
up into the C40 ‘waxes’ and larger n > 40 ‘asphaltenes’). It is cracking processes.43,44 These fragmentation reactions
thus reasonable that the distillates from the waste grease BC are important for fuel production because they convert
comprise classes of small (gasoline-sized, ~C3-C8), medium higher molecular weight, less-volatile compounds (e.g.,
(jet-sized, ~C9-C13), and large (diesel-sized, ~C14-C20) size the FFAs and ketone dimer) into lower molecular weight,
fuel compounds similar to that received from petroleum more-volatile compounds, with the majority of the fuel
crude. compounds devoid of oxygen. Three hundred sixteen
stainless steel, Hastelloy, Inconel, and titanium tubular metal
Supercritical water and the null reactor reactors (1 cm i.d, 15 cm length) were employed in separate
studies and all had no detectable mass loss after repeated use
Our mechanistic studies also provided information about
of 16 h or more of processing time (173.5 g, 228.2 g, 208.1 g,
the role that SCW may be playing in the conversion of
and 173.6 g, all showed ±0.3 g before and after long use,
BG FS into fuel compounds. The ‘null reactor’ run, a
respectively). Thus, any of these metal materials would be
reactor devoid of catalyst, resulted in a reactor that was
acceptable for long-term reactor use. For all of the reactor
quickly plugged (within minutes of running FS) with black
and tubing materials scaled-up pilot plant level we are
char when temperatures reaching 450 °C were attained.
planning to use 316 stainless steel.
Running pure FS without any additional SCW also plugged
quickly at around 400 °C. Hence, processing the FS at high
temperatures (>500 °C) without catalyst or without SCW is
Desulfurization
simply not possible within this flow system. We observed Supercritical water also appears to play an important role
fragmentation of all the model compounds at the optimal in lowering the levels of sulfur in the BC liquid produced
temperature (550 °C) in SCW. This fragmentation even in the titania reactor. Our model compound studies with
occurred with stable hydrocarbons like octane, hexadecane, octanethiol showed that hydrogen sulfide (H2S) was the main
Table 3. Biocrude product compounds from processing pure oleic acid (GCMS analysis).
R.T. Compound name % Qual. R.T. Compound name % Qual.1.
1.206 Propene 0.057% 90% 3.422 1-ethylcyclopentene 0.214% 53%
1.246 2-methylpropene 0.208% 90% 3.487 1,3-cycloheptadiene 0.057% 81%
1.257 1-butene 0.088% 90% 3.641 1-octene 1.437% 96%
1.323 2-methylbutane 0.013% 58% 3.733 1,2-dimethylcyclohexane 0.173% 95%
1.346 1-pentene 0.291% 90% 3.787 octane 0.820% 91%
1.353 pentane 0.200% 78% 3.915 2(E)-octene 0.379% 95%
1.380 2-pentene 0.121% 90% 3.970 4-methyl-1,3-heptadiene 0.153% 87%
1.396 2-methyl-2-butene 0.138% 91% 4.059 4-(Z)octene 0.331% 94%
1.432 1,3-pentadiene 0.105% 94% 4.121 1-ethylcyclohexene 0.065% 80%
1.463 1,3-cyclopentadiene 0.153% 81% 4.172 spiro[2.5]octane 0.219% 91%
1.507 cyclopentene 0.248% 91% 4.238 3,5-diemethylcyclohexene 0.231% 91%
1.616 1-hexene 0.873% 94% 4.305 1,6-dimethylcyclohexene 0.142% 89%
1.651 Hexane 0.489% 91% 4.388 ethylcyclohexane 0.313% 81%
1.684 3-hexene 0.514% 91% 4.469 3-ethylidenecyclohexene 0.069% 93%
1.731 2-hexene 0.509% 70% 4.504 methylethylcyclopentene 0.199% 87%
1.811 methylcyclopentane 0.304% 81% 4.632 1,5-dimethylcyclohexene 0.269% 93%
1.897 1-methyl-1,3-cyclopentadiene 0.209% 93% 4.690 4-octyne 0.225% 64%
1.933 1,3-cyclohexadiene 0.171% 81% 4.810 3(Z),5(Z)-octadiene 0.061% 87%
1.971 1-methylcyclopentene 0.691% 90% 4.860 2,4-octadiene 0.411% 93%
2.009 2(E),4(E)-hexadiene 0.249% 95% 4.968 2,4,6-octatriene 0.109% 94%
2.055 benzene 0.684% 95% 5.003 ethylbenzene 0.753% 91%
2.117 5-methyl-1,3-cyclopentadiene 0.168% 86% 5.095 1,4-bis(methylene)cyclohexane 0.207% 78%
2.201 cyclohexene 0.686% 93% 5.150 1-ethylcyclohexene 0.592% 94%
2.284 1-heptene 1.541% 96% 5.185 p-xylene 0.515% 97%
2.369 heptane 0.953% 91% 5.239 4,5-nonadiene 0.296% 60%
2.413 2,3-dimethyl-1,3-pentadiene 0.307% 70% 5.632 1-nonene 0.203% 97%
2.452 2-heptene 0.520% 94% 5.658 o-xylene 2.009% 90%
2.543 3-heptene 0.546% 93% 5.817 nonane 0.688% 64%
2.634 methylcyclohexane 0.481% 94% 5.961 2(E)-nonene 0.598% 96%
2.732 3-methyl-1,3(E),5-hexatriene 0.050% 86% 6.038 2-nonyne 0.164% 58%
2.776 ethylcyclopentane 0.315% 94% 6.130 2-(Z)-nonene 0.343% 96%
2.853 2-heptyne 0.444% 91% 6.194 bicyclo[3.2.1]nonane 0.131% 50%
2.902 1,3(E),5(E)-heptatriene 0.145% 93% 6.357 3-methyl-2-methy-1,3-hexadiene 0.266% 59%
2.911 1-methyl-1,4-cyclohexadiene 0.170% 92% 6.447 propylcyclohexane 0.212% 55%
3.000 1,3-bis(methylene)cyclopentane 0.150% 87% 6.545 butylcyclopentane 0.263% 96%
3.025 1-methyl-2,4-cyclohexadiene 0.136% 92% 6.645 1-methyl-6-methylenebicyclo[3.2.0]heptane 0.208% 62%
3.066 (1-methylethylidene)cyclobutane 0.189% 87% 6.784 1-methylbicyclo[3.2.1]octane 0.103% 76%
3.093 ethylidenecyclopentane 0.638% 91% 6.827 5,5-dimethyl-1,3-heptadiene 0.076% 60%
3.199 bicyclo[4.1.0]hept-2-ene 0.127% 90% 6.876 1-butylcyclopentene 0.581% 81%
3.263 toluene 1.452% 94% 6.938 4-nonyne 0.156% 87%
3.299 1-methylcyclohexene 0.935% 90% 6.992 Ethylidenecycloheptane 0.170% 58%
3.422 1-ethylcyclopentene 0.214% 53% 7.034 Propylbenzene 0.360% 81%
3.487 1,3-cycloheptadiene 0.057% 81% 7.111 1-propylcyclohexene 0.270% 90%
3.641 1-octene 1.437% 96% 7.160 1-butenylcyclopentane 0.113% 87%
3.733 1,2-dimethylcyclohexane 0.173% 95% 7.230 1-ethyl-3-methylbenzene 0.241% 81%
Table 4. Continued biocrude products from processing pure oleic acid (GCMS analysis).
R.T. Compound name % Qual. R.T. Compound name % Qual.
7.257 1-ethyl-2-methylbenzene 0.265% 70% 11.511 2(E),4(E)-undecadiene 0.266% 90%
7.425 1-cyclohexylethanone 0.438% 70% 11.552 pentylbenzene 0.574% 76%
7.537 4-octanone 0.229% 86% 11.642 1,2,3,4-tetrahydronaphthalene 0.737% 80%
7.637 1,2,4-trimethylbenzene 0.366% 90% 11.774 1-methyl-4-(2-methylpropyl)benzene 0.389% 64%
7.818 3-octanone 0.441% 53% 11.892 5-decanone 0.240% 94%
7.882 1-decene 0.505% 95% 11.952 1-methyl-4-(1-methylpropyl)benzene 0.218% 64%
7.917 2-octanone 0.715% 91% 12.071 2,3-dimethyl-1H-indene 0.209% 70%
7.951 1,2,3-trimethylbenzene 0.322% 91% 12.245 1-dodecene 0.930% 95%
8.037 bicyclo[5.3.0]decane 0.284% 55% 12.326 2-dodecanone 0.867% 86%
8.071 decane 0.318% 95% 12.413 dodecane 0.412% 90%
8.211 4(E)-decene 0.472% 96% 12.530 2-dodecene 0.416% 95%
8.324 2,3,4,5,6,7-hexahydro-1H-indene 0.208% 70% 12.711 5-dodecene 0.322% 93%
8.392 4(Z)-decene 0.452% 97% 12.964 4-ethenylcycloctene 0.253% 78%
8.542 4-methyl-1-(1-methylethyl)cyclohexene 0.436% 83% 13.004 hexylidencyclohexane 0.168% 94%
8.682 1,1’-bicyclopentyl 0.199% 60% 13.096 cyclododecene 0.164% 68%
8.753 trans-2,3-dimethylbicyclo[2.2.2]octane 0.168% 78% 13.153 5(E),7(E)-dodecadiene 0.196% 58%
8.880 cycloproylbenzene 0.467% 76% 13.200 1-hexylcyclohexene 0.695% 58%
8.948 1-(3-butenyl)-1,3-cyclopentadiene 0.211% 95% 13.330 (E)-cyclododecene 0.253% 70%
9.037 2,3-dimethyl[2.2.2]bicycloctane 0.116% 68% 13.405 5(Z),7(Z)-dodecadiene 0.356% 76%
9.138 1-pentylcyclopentene 0.411% 81% 13.464 5(Z),7(E)-dodecadiene 0.370% 80%
9.178 1-butylcyclohexene 0.273% 70% 13.568 2(E),4(Z)-dodecadiene 0.321% 87%
9.231 1,3-diethylbenzene 0.144% 60% 13.754 1,3-dimethyl-1H-indene 0.154% 64%
9.347 butylbenzene 0.391% 64% 14.062 4-(2-butenyl)-1,2-dimethylbenzene 0.177% 70%
9.528 propylidenecyclohexane 0.433% 76% 14.252 2-tridecene 0.695% 95%
9.600 (1-methylpropyl)benzene 0.215% 50% 14.345 2-undecanone 0.493% 93%
9.752 4-nonanone 0.251% 70% 14.405 tridecane 0.284% 89%
9.839 2-ethyl-1,4-dimethylbenzene 0.163% 76% 14.512 3-tridecene 0.382% 60%
9.883 1,2,3,5-tetramethylbenzene 0.221% 53% 14.692 2-tridecene 0.294% 87%
10.011 1-phenyl-1-butene 0.439% 90% 14.868 2,3-dihydro-1,1,3-trimethyl-1H-indene 0.146% 94%
10.055 3-nonanone 0.348% 92% 14.931 6-tetradecyne 0.240% 80%
10.121 1-undecene 0.780% 96% 15.061 5-undecyne 0.174% 58%
10.181 2-nonanone 0.530% 94% 15.149 7(E),9(E)-dodecadienal 0.147% 52%
10.242 4-undecene 0.547% 86% 15.265 2-methyl-7-pentylbicyclo[4.1.0]heptane 0.345% 60%
10.298 undecane 0.332% 86% 15.413 1-octylcyclopentene 0.295% 93%
10.357 3-methyl-6-(1-methylethyl)cyclohexene 0.164% 64% 15.462 7(Z),9(Z)-dodecadienal 0.224% 94%
10.429 5-undecene 0.976% 98% 15.591 3-methyl-7-pentylbicyclo[4.1.0]heptane 0.184% 68%
10.503 2,6-dimethylbicyclo[3.2.1]octane 0.160% 53% 15.636 1,9-dimethylspiro[5.5]undecane 0.297% 90%
10.607 3-undecene 0.701% 97% 15.806 6-dodecanone 0.459% 96%
10.714 decarbo-2-methylnaphthalene 0.164% 78% 16.142 2-tetradecene 0.587% 95%
10.879 1,6-cyclodecadiene 0.415% 89% 16.380 E-3-tetradecene 0.417% 89%
10.925 2-butylbicyclo[2.2.1]heptane 0.192% 64% 16.565 3(Z)-tetradecene 0.250% 90%
11.018 pentylcyclohexane 0.153% 55% 17.155 nonylcyclopentane 0.361% 87%
11.151 pentylidenecyclohexane 0.282% 70% 17.286 1-heptylcyclopentene 0.696% 80%
11.295 1-methyldecahydronaphthalene 0.387% 87% 17.494 1-octylcyclohexene 0.666% 94%
11.357 2(Z),4(E)-undecadiene 0.246% 81% 17.611 6-tridecanone 0.347% 70%
Table 5. The remaining biocrude products from processing pure oleic acid (GCMS analysis).
R.T. Compound name % Qual. R.T. Compound name % Qual.
17.683 5-nonadecen-1-ol 0.149% 83% 21.224 1-heptadecene 0.240% 99%
17.879 1-hexadecanol 0.116% 60% 21.272 2-methylcycloundecane 0.210% 90%
17.931 cyclopentadecane 0.423% 98% 21.338 7-pentadecyne 0.206% 96%
18.053 pentadecane 0.378% 86% 21.367 2-pentadecanone 0.233% 55%
18.138 1-hexadecyne 0.451% 81% 21.598 3(E)-heptadecene 0.147% 95%
18.336 decylcyclopentane 0.222% 64% 22.294 10(E),12(E)-hexadecadien-1-ol 0.188% 86%
18.397 6,10-dimethyl-1,6-dodecadien-12-ol 0.315% 59% 23.850 11(E)-hexadecen-1-ol 0.292% 93%
18.691 1,2-dimethylcycloctene 0.154% 70% 23.946 2(E),13(E)-octadecadien-ol 0.322% 93%
18.940 n-nonylcyclohexane 0.431% 87% 24.012 2(Z),13(Z)-octadecadien-ol 0.321% 89%
19.027 2-methyl-7-octadecyne 0.386% 80% 24.110 1-hexadecyne 0.329% 64%
19.096 n-octylidencyclohexane 0.140% 86% 24.195 1,11(E),13(Z)-octadecatriene 0.233% 55%
19.181 1,6(Z)-tridecadiene 0.209% 91% 24.298 2-butyl-5-hexyloctahydro-1H-indene 0.191% 86%
19.207 (E)-pinane 0.215% 95% 24.352 2-heptadecanone 0.512% 93%
19.281 1-heptylcyclohexene 0.428% 81% 25.279 E-bicyclo[10.8.0]eicosane 0.266% 83%
19.321 1,9(E)-tetradecadiene 0.567% 93% 25.388 bicyclo-(Z)-[10.8.0]eicosane 0.379% 87%
19.383 1,15-hexadecadiene 0.776% 96% 25.666 3-octadecanone 0.149% 72%
19.623 1-hexadecene 0.472% 94% 25.756 methyl-n-hexadecyl ketone 0.144% 58%
19.639 1-methyl-2-methylenecyclohexane 0.589% 92% 27.087 2-nonadecanone 0.886% 99%
19.828 7(Z)-hexadecene 0.312% 86% 27.712 methyl-8,11-octadecadienoate 0.272% 80%
20.008 3(Z)-hexadecene 0.320% 91% 27.795 9(Z),12(Z)-octadecadienoic acid 0.028% 90%
20.234 2-tetradecyne 0.206% 81% 27.949 3(E),13(E)-octadecadien-ol 0.428% 68%
20.771 11,13-hexadecadien-1-ol 0.172% 72% 28.038 3(Z),13(Z)-octadecadien-1-ol 0.814% 56%
20.871 1,11-dodecadiene 0.473% 94% 28.282 3-eicosanone 0.182% 72%
20.979 1(Z),9(Z)-tetradecadiene 0.894% 89% 30.246 3(Z),13(E)-octadecadien-1-ol 0.260% 91%
21.095 8-heptadecene 0.656% 98% 42.277 18-pentatriacontanone (C35) 0.392% 99%
sulfur-containing by-product formed in the reactor. This is Engine Research Lab. Standardized engines compared
consistent with other reports in the literature, which have the biofuels with pure petroleum counterpart fuels. The
suggested that organosulfur species decompose in SCW via a engines were a BMW, W-20, spark ignition (SI) engine;
radical-based mechanism.45 We observed that desulfurization Capstone, 30 kW, microturbine generator; and a John
occurred faster than thermal cracking of hydrocarbons, Deere, 10 hp, single cylinder diesel engine. Two different
which can be explained by the lower bond dissociation energy electrical generator loads were applied to each engine
(BDE) and faster homolytic cleavage of the sulfur-carbon while computer-controlled fuel delivery to the engines
bond (S–Csp3 BDE ca. 70 kcal•mol−1). The conversion to maintained the electrical torque loads (for engines: torque
largely a single, gaseous sulfur-containing by-product (H2S) × RPM = power) with the dynamometers. Engine tests were
and, importantly therefore, one that is not a component of run and the performance and exhaust emissions (i.e., NOx,
the BC, is economically advantageous from the perspectives CO, CO2 and H2O, and non-combusted hydrocarbons)
of both remediation (sulfur capture) and fulfilling ASTM fuel were measured continuously during the load testing for
specifications. Titania-catalyzed loss of H2S to produce an each engine. The biofuels ran the engines with reproducibly
alkene by a polar, ionic mechanism is also a possible route by stable and steady fuel consumption rates, RPM values,
which desulfurization occurs. and exhaust emissions (±3%). The average biofuel and
bioblended fuel engine test results are shown in Table 6.
All 5% bioblended fuels had statistically identical power
Engine testing
output performance levels to those of the associated
The biofuels created from the distilled BC fractions were petroleum fuels (relative standards). The green jet fuel
tested in engines at the University of Minnesota Murphy showed 94.4% power performance (measured with an engine
Table 6. Relative power performance output Table 8. Specific ASTM test values for 5% and
levels of the green fuels (and 5% blends) in test 50% bioblends of green jet fuel.
engines versus comparable all-petroleum fuels, Jet (D7566) 5% 50% ASTM
based on the same fuel mass flow rates (g/min.).
Blend Blend Jet
Green fuels/engines: % Engine power output
ASTM Test Value Value Spec.’s
5% Bioblend: 100% Green
D3242 Acid 0.00 0.01 <0.10
fuel:
a.
Green gasoline/SI Engine (vs. 91-octane, non-oxy petroleum) D6379 Arom. 18.83 19.67 <26.5%
Mode 1 (2400 RPM, 15 kW) 100.8% 107.7% D56 Flash Pt. 49 42 >38 °C
Mode 2 (3000 RPM, 15 kW) 100.7% D4052 Density 0.8121 0.8133 0.77-0.84
b.
Green jet/turbine Engine (vs. jet A petroleum) D2386 Freeze pt. (°C) −58 −78 <−40
Mode 1 (15 kW load) 101.5% 94.4% D445 Kin. visc. 5.05 3.015 <8.0
Mode 2 (20 kW load) 100.0% D1322 Smoke pt. 22 18.5 >18.0

c.
Green diesel/diesel engine (vs. #2 diesel, non-bio petroleum) D1840 Naphthal. 0.51 0.79 <3.0
Mode 1 (2000 rpm, 15 nm load) 100.9% 101.3% D130 Cu corr. 1 1 ≤1
Mode 2 (2500 rpm, 9 nm load) 100.3% D381 Gum 2 5 <7
Uncertainties: a. ± 0.07%, b. ± 0.20%, c. ± 2.1% D3948 H2O Sep. 100 83 >70

D2624 Conduct. 195 228 <450
D5453 Sulfur (ppm) 0.67 3.36 <3000
Table 7. Specific ASTM test values for 5% D86 Dist.(10%,°C) 182.3 146.3 <205
bioblend and 100% green gasoline. D86′ Dist.(final,°C) 278.5 269.3 <300
Gasoline (D4814) 5% 100% ASTM D86″ Dist. residue 1.3 1.3 <1.5%
Blend Gas
Table 9. Specific ASTM test values for a 5%
D130 Cu corr. 1A 1A ≤1
bioblend and 100% (pure) green diesel fuel.
D2699 RON 92.6 88.6 Report
Diesel (D975) 5% 100% ASTM
D2700 MON 87.2 81.6 Report
Blend Diesel 2
D4814 (R+M)/2 89.9 85.1 >85.02
D3237 Pb (lead) < 0.001 < 0.001 <0.05
D130 Cu corr. 1A 1A ?3
D381 Gums < 0.5 4.0 <5.0
D2500 Cloud Pt. °C –21 –49 Report
D3831 Mn < 0.2 < 0.2 Report
D2709 H2O/Sed. < 0.005 < 0.005 <0.05
D4052 Sp.gr. 0.719 0.743 Report
D445 Kin. Visc. 2.491 2.503 1.9–4.1
D5188 Vap:Liq(°F) 148.9 156.8 >95
D482 Ash < 0.001 < 0.001 <0.01
D5191 R.V.P. 8.67 7.40 7.8-15.0
D525 10%Rmsbtm 0.13 0.26 <0.35
D525 O2 stab. 1440 750 >240
D5453 Sulfur (ppm) 4.37 10.54 <15
D5453 Sulfur 1.40 2.93 <80
D6079 Lubricity 330 450 <520
D5599 Oxygates < 0.1 < 0.1 Report
D613 Cetane # 41.6 46.4 >40
D7681 Ag corr. 0 0 ≤1
D6591 Arom./mid 36.65 33.06 <65%
D86 Dist.(50%,°F) 221.9 190.6 170-250
D86 Dist.(90%,°C) 323 248 >338
D86′ Dist.(90%,°F) 334.2 257.7 <365
D664 Acid 0.00 0.00 <0.3
D2624 Cond. (pS/m) 502 538 >25
dynamometer) compared with Jet A when unblended at
D93 Flash Pt. (°C) 107 96 >52 °C
100%, while the unblended, neat green gasoline showed
107.7% power performance levels compared to 91-octane
petroleum gasoline, and the neat green diesel showed 101.3%
power performance compared to petroleum diesel #2. We
ASTM fuel specifications
plan to produce larger quantities of these biofuels (>10 gal) The three green biofuels were tested (at 5% and 100%
at the pilot-plant scale and evaluate their performances and levels for green gasoline and green diesel, and 5% and
emissions in larger automobile and farm-sized engines. 50% blends for green jet) with petroleum ASTM methods
(D4814 – gasoline; D7566 – jet; D975 – diesel). Tables 7–9 triglycerides when processing at 350-550 °C. These ketones
show the ASTM data alongside the maximum/minimum were further degraded into biofuel compounds of alkane,
values needed to pass the fuel specification standards. alkene, and aromatic classifications at higher processing
For example, the green gasoline/jet/diesel fuels that were temperatures. More than 16 kg of BG/YG were processed
produced showed ASTM sulfur levels of 2.9/3.4/10.5 ppm, under SCW conditions into BC and then distilled and refined
respectively; with the maximum limits of the analogous into approximately 4 gal of biofuels that were analyzed to
petroleum fuels at 15/3000/15 ppm, respectively. So, all were determine the mass balance of the input FS into liquid and
below the sulfur specification limit, but the green jet value gaseous biofuel output products. The BC was distilled into
is nearly three orders of magnitude below. This result is fractions and mixed accordingly into the green gasoline,
remarkable considering the initial sulfur concentration of the green jet, and green diesel fuels. These biofuels were tested
BG was 1230 ppm! One important test for jet fuel is the total in appropriate engines and showed 97–108% power output
oxidation test (JFTOT, D3241). Besides the high cost, this performance levels and lower exhaust emissions (compared
test requires over 3 L of fuel for the test, so that is a planned with the respective pure petroleum fuels). The biofuels were
test after the pilot scale is complete and more fuel can be also analyzed using petroleum ASTM quality methods
readily processed. All green fuels passed the Cu corrosion and passed all specifications measured. After ‘coking’, the
(D130) test, which is important for long term use with engine titania catalyst was shown to be fully regenerable to its
metals and the green gasoline also passed the required Ag original color and catalytic activity. The output water phase
metal corrosion (D7681) test. The green jet and diesel had was demonstrated to work when recycled back through
outstanding cold temperature properties (−78 and −49 °C in the system. The desulfurization that occurred, largely with
D2386 and D2500 tests, respectively) that were lower than hydrogen sulfide product, gave biofuels that passed the low-
the 5% bioblends (−58 and −21 °C, respectively). The 5% sulfur fuel ASTM specifications even starting from waste
bioblend values, with 95% petroleum, would be close to the brown and yellow greases of high sulfur content. Further
pure petroleum values themselves. Maintaining fuel liquidity work is planned to scale up the production so larger volumes
is very important for high altitudes (colder climates) and of green gasoline, green jet, and green diesel biofuels can be
the green fuels performed better than the petroleum fuels studied in further ASTM specifications, such as the JFTOT
themselves. We summarize that green gasoline and green (for green jet), and used to run in higher horsepower test
diesel could be used as direct drop-in fuels, unblended, with engines like BMW automobile, Capstone turbine/jet, and John
their ASTM results and the 108% and 101% power output Deere tractor-sized engines.
performances compared with 91-octane and #2 road diesel,
while green jet fuel could be used as a 50% blend and attain
Acknowledgements
97% power output performance relative to Jet A. The current
FFA-mandated maximum level of renewable biofuel in The authors would like to acknowledge the financial
blended jet fuel is 50%, but it is reasonable to expect that the support of the Department of Energy and its Office of
restriction could ease if a track record of proven performance Biotechnology (Grant number DE-SC0018792) and the
grows. United States Department of Agriculture (Grant number
2018‐33610‐28259). We would also like to acknowledge
Conclusion Darrick Zarling who directed and helped perform the green
fuels engine tests and then prepared the data reports and
In this work the hydrothermal catalytic SCW conversion of the assistant researchers at the University of Minnesota TE
waste brown and yellow greases (BG/YG) into green gasoline, Murphy Engine Research Laboratories.
jet, and diesel biofuels was investigated. The SCW process
conditions were optimized in regard to the BC products
produced with the varied catalysts, BG/YG:SCW feed ratios,
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(2006). Clayton V. McNeff
42. Poutsma ML, Free-radical Thermolysis and Hydrogenolysis Clayton V. McNeff received his BS
of model hydrocarbons relevant to processing of coal. Energy
in chemistry (1991) from Augsburg
Fuel 4(2):113–131 (1990).
College in Minneapolis, Minnesota,
43. Berkowitz N and Calderon J, Extraction of oil sand Bitumens
with supercritical water. Fuel Process Technol 25(1):33–44 and a PhD in analytical chemistry at
(1990). the University of Minnesota (1996). He
44. Cheng Z-M, Ding Y, Zhao L-Q, Yuan P-Q and Yuan W-K, is the CEO of ZirChrom Separations,
Effects of supercritical water in vacuum residue upgrading. the VP and Director of Research of
Energy Fuel 23(6):3178–3183 (2009). SarTec Corporation, CSO of Mcgyan Biodiesel LLC
45. Patwardhan PR, Timko MT, Class CA, Bonomi RE, Kida Y, and CSO/CFO of Ever Cat Fuels, LLC. Dr. McNeff
Hernandez HH et al., Supercritical water desulfurization of has authored more than 25 peer-reviewed scientific
organic sulfides is consistent with free-radical kinetics. Energy publications and has 42 issued patents as well as 3
Fuel 27(10):6108–6117 (2013).
pending patents. He has led research on the synthesis
and use of zirconia-based liquid chromatographic
stationary phases. He is the co-inventor of the patented
Mcgyan process, which uses ‘green’ chemical processes
that are useful for the continuous production of biodiesel
Ronald L. Fedie
fuel. He has been the principal investigator for numerous
Ronald L. Fedie is currently the competitive research grants funded by the National
Biofuels Processing and Research Science Foundation (NSF), National Institutes of Health
Director at SarTec Corporation. He (NIH), United States Department of Agriculture (USDA)
received his BS degree in chemistry and Department of Energy (DOE). He is a recipient of
(1989) from St Thomas University the national Tibbett’s Award associated with federal
performing chemilluminescent SBIR programs as well as four Commendations for
research with Dr. Joseph Brom, Entrepreneurial Spirit and Innovation from the State of
and a PhD in chemistry (1995) from the University of Minnesota. He is a member of the American Chemical
Minnesota, specializing in physical/polymer chemistry, Society, the American Oil Chemists’ Society and the
under the direction of Dr Wilmer G. Miller. Professor Minnesota Chromatography Forum. He authored a book
Fedie taught general, physical, and polymer chemistry entitled The Green Miracle.
at Knox College and then Augsburg University (along
with physical chemistry in summer terms at the
University of Minnesota) where he highlighted chemical
demonstrations and performed professor-student
Charles V. McNeff
research presented at local, regional, and national
american chemical society (ACS) meetings. After Charles V. McNeff is currently a
21 years of academia, Dr Fedie became a Senior R&D graduate student working on his
Scientist at SarTec in 2016, with his research focused on PhD in organometallic chemistry in
catalytic biofuels synthesis, biomass treatment, biofuel the chemistry department at North
property analyses, and biofuel process engineering. Dakota State University. He has also
He has helped to obtain and manage United States worked and performed research at
Department of Agriculture (USDA) and Department of the SarTec corporation, assisting with
Energy (DOE) small business innovation research (SBIR) the catalytic conversion of biomass into bioproducts and
grants to support the research and was issued a patent biofuels, and he has four patents. Charles received his
on catalytic biomass conversion. BS in chemistry from Augsburg University.
Larry C. McNeff Bingwen Yan

Larry C. McNeff is President of Bingwen Yan has retired from the
SarTec Corporation, a company SarTec Corporation, but while there
he co-founded in 1983. SarTec he conducted research related to
manufactures natural, Yucca- biofuels and helped to develop
based products for use in varying analytical methods for product quality
applications, including lawn care, control from 2001. Dr. Yan was
animal health and feed additive, one of the inventors of the Mcgyan
grain conditioning and waste management control. Biodiesel technology, holds several patents, and has
Larry McNeff is also president of Marla Properties (a published more than 50 articles in chromatography,
real estate ownership and management company), MA separation science, catalyst, biofuel, and material
Properties (a real estate ownership and management science. He was previously a visiting professor in the
company) and President of McNeff Research chemistry department at the University of Minnesota,
Consultants. He is the Chief Manager of Ever Cat Fuels, and a professor at Nankai University, where he was an
which owns and operates a 3 million gallon per year associate director in the analytical division of the State
biodiesel plant located in Isanti, MN. He is also the Chief Key Laboratory of Elemento-Organic Chemistry. Dr Yan is
Manager of Mcgyan Biodiesel LLC, which offers turnkey a member of the American Chemical Society and received
biodiesel plants. He holds a chemistry degree from his BS in chemistry from Hunan Normal University, and a
the University of Nebraska where he also conducted PhD in organic chemistry from Nankai University (China).
graduate research work as a lab assistant. He holds
nine patents for work completed at Cargill and SarTec
Corporation. Previous positions have included Marketing
Director for Wingrove Enterprises, Silo Guard, and
various positions in chemistry and laboratory work for Julie A. Jenkins
Cargill, Inc. He is a member of the American Chemical
Society and American Society of Animal Science. Julie A. Jenkins graduated with a
bachelor’s degree in chemistry (2009)
from Augsburg College, and a PhD in
chemistry (2017) from the University of
Connecticut. Dr. Jenkins thesis work
focused on the optical interaction of
Peter G. Greuel gold nanoparticles and quantum dots
Peter G. Greuel received a BS in and their application in a polymer hydrogel modified
chemistry (1990) and a BBA in lateral flow sensing device. She worked as a quality-
operations management (1990) from control chemist and laboratory manager at Ever Cat
the University of Wisconsin Oshkosh. Fuels, and as a Research Scientist and General Manager
He also received a PhD in materials of SarTec Corporation.
chemistry from the University of
Minnesota (1996) where he studied
the mechanisms involved in plasma assisted chemical
vapor deposition of thin diamond films. Dr Greuel is
currently the General Manager of SarTec Corporation
in Anoka, MN, where he manages all the company’s
operations.
Jason T. Brethorst Thomas R. Hoye

Jason T. Brethorst received his BS Thomas R. Hoye received the
in chemistry (2011) from St Cloud bachelor of science and master of
State University. There, he worked science degrees in chemistry from
with Professor Mark Mechelke Bucknell University in 1972 under
on a research project aimed at the guidance of Professor Harold W.
discovering structurally simplified Heine. He then carried out his PhD
chemotherapeutic compounds through thesis research in organic chemistry in
the synthesis of natural product analogs. He received his the laboratory of Professor Robert B. Woodward. Since
PhD in organic chemistry from the University of Minnesota 1976, he has spent his entire career as a faculty member
(2017) under the tutelage of Professor Christopher in the Department of Chemistry at the University of
Douglas. While a graduate student at the University of Minnesota, where he is currently Distinguished Professor
Minnesota, he undertook research projects centered on of Science and Engineering. His research group pursues
the development of metal-catalyzed bond activation and studies of mechanistic, synthetic, structural, and
functionalization methodologies, and the application of spectroscopic organic, natural product, medicinal, and
these methodologies towards the synthesis of natural polymer chemistries.
products. He later worked with Professor Thomas Hoye at
the University of Minnesota as a Postdoctoral Researcher
(2019), where he explored the application of supercritical
fluids and metal oxide catalysis towards the production
of renewable biofuels. He is currently a Professor of
chemistry at Anoka Ramsey Community College.
Grant B. Frost
Grant B. Frost earned his BS in
chemistry (2011) from the University
of St Thomas in St Paul, Minnesota,
and a PhD in chemistry (2019) from
the University of Minnesota under the
advisement of Professor Christopher
J. Douglas. During his graduate
research career, he published multiple papers in the field
of organometallic catalysis applied to small molecule
synthesis. After graduating he worked as a postdoctoral
associate under the supervision of Professor Thomas
R. Hoye at the University of Minnesota. There he
collaborated with Sartec Corporation on the green
synthesis of biofuels from biomass via continuous flow
metal oxide-catalyzed processes in supercritical water.
He is currently a Postdoctoral Fellow at Northwestern
University in Evanston, IL, under the supervision of
Professor Karl A. Scheidt.

Biofuels Bioprod Bioref - 2021 - Fedie - Hydrothermal Catalysis of Waste Greases Into Green Gasoline Jet and Diesel

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In the Field

Hydrothermal catalysis of waste

Received November 06 2020; Revised November 08 2021; Accepted November 10 2021;

were remarkably similar, suggesting that similar mechanisms

Reaction process runs to optimize

Figure 7. Comparison of fresh and regenerated catalyst.

Distillation of the biocrude liquid into fuel

Compound class composition of biofuel

Mode 2 (20 kW load) 100.0% D1322 Smoke pt. 22 18.5 >18.0

Mode 1 (2000 rpm, 15 nm load) 100.9% 101.3% D130 Cu corr. 1 1 ≤1

Mode 2 (2500 rpm, 9 nm load) 100.3% D381 Gum 2 5 <7

Uncertainties: a. ± 0.07%, b. ± 0.20%, c. ± 2.1% D3948 H2O Sep. 100 83 >70

compressed water. Energ Conver Manage 47(18):3344–3350

Larry C. McNeff Bingwen Yan

Jason T. Brethorst Thomas R. Hoye

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