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6586 r2010 American Chemical Society pubs.acs.

org/EF
Energy Fuels 2010, 24, 65866600
:
DOI:10.1021/ef101154d
Published on Web 11/09/2010
Red Mud as a Catalyst for the Upgrading of Hemp-Seed Pyrolysis Bio-oil
Elham Karimi,

Cedric Briens,
,
Franco Berruti,
,
Sina Moloodi,
)
Tommy Tzanetakis,
)
Murray J. Thomson,
)
and Marcel Schlaf*
,

Department of Chemistry, The Guelph-Waterloo Centre for Graduate Workin Chemistry (GWC)
2
, University of Guelph, Guelph,
Ontario N1G 2W1, Canada,

Department of Chemical and Biochemical Engineering, University of Western Ontario, London,
Ontario N6A 5B9, Canada,

Institute for Chemicals and Fuels from Alternative Resources (ICFAR), 22312 Wonderland Road
North, RR#3, Ilderton, Ontario N0M 2A0, Canada, and
)
Department of Mechanical and Industrial Engineering, University of
Toronto, 5 Kings College Road, Toronto, Ontario M5S 3G8, Canada
Received August 26, 2010. Revised Manuscript Received October 20, 2010
Hemp-seed pyrolysis bio-oil was upgraded in a batch laboratory-scale pressure reactor under 800 psi (cold)
hydrogen gas at 350-365 C using a non-alkaline, nontoxic Fe
x
O
y
/SiO
2
/TiO
2
catalyst [reduced red mud
(RRM)] obtained by the reduction of red mud with HOAc/HCCOH. The upgraded liquid obtained was
separated into stable organic and aqueous phases. Comparative analyses between the crude oil and the
organic and aqueous phases of upgraded products showed that the RRM-upgraded bio-oil is composed of
fewer carbonyl-containing and polar oxygenated compounds but more saturated hydrocarbons. The
upgraded oil phases are less viscous than the native oil and stable against resin formation for at least
60 days. The catalytic activity of RRMis related to its ability to catalyze both deoxygenation and cracking
reactions that convert reactive components (aldehydes, ketones, and carboxylic acids), which make the oil
unstable over time, into less reactive deoxygenated products.
Introduction
Bio-oil obtained by fast pyrolysis of lignocellulosic or
other biomass is a complex mixture of alcohols, furan and
pyran derivatives, aldehydes, ketones, esters, lactones, free
carboxylic acids, phenols, and catechols.
1-3
It is typically
characterized by high water (15-30%, w/w) and oxygen
(40%, w/w) contents and low pH (2.5 on the aqueous
scale) caused by the presence of carboxylic acids (mainly
formic and acetic acids), as well as phenols and catechols
originating from the lignin portion of the feedstock used. The
combination of the reactive carbonyl components with phe-
nols, acid, and water make the oil corrosive, difficult to ignite
and burn cleanly, and unstable against condensation and
carbon-carbon bond-forming cross-linking reactions. These
reactions canresult in resinformationandphase separation of
an aqueous phase triggered by the generation of additional
water. Scheme 1 illustrates some of the conceivable reaction
pathways of this process (notably phenol resinformation
4
and
aldol condensations), which renders typical bio-oils unsuit-
able for direct use as fuel and makes their longer term storage
problematic.
The actual use and storage of pyrolysis bio-oil as a fuel or
petrochemical feed therefore requires its stabilization through
a reductive catalytic upgrading process that (a) raises the pH
of the oil by converting the carboxylic acids present into non-
acidic and noncorrosive products that can no longer act as a
catalyst for the reactions of Scheme 1, (b) hydrogenates the
reactive aldehyde and ketone components into alcohols that
can no longer undergo aldol condensations while enabling
esterification/etherification of any excess acids/phenols pres-
ent, thus further lowering the acidity and overall reactivity of
the bio-oil, and (c) lowers the overall oxygen and water
content of the oil by eliminating CO
2
and water, which ideally
would phase separate from an upgraded organic oil phase of
higher energy density that is then also stabilized against resin
formation.
Considering the prevalence of formic and acetic acids in a
typical bio-oil, Scheme 2
5
summarizes the main reaction
pathways requiredtomeet the objectives (a-c) laidout above,
in which the decomposition of formic acid, if present in
sufficient amounts, can serve as an internal source of hydro-
gen and the ketonization of acetic acid (or other carboxylic
acids) serves as an efficient decarboxylation pathway. The
decomposition of formic acid is intrinsically viable at high
temperatures (.400 C)
6
but benefits from the presence of a
catalyst,
7,8
while the also required acid ketonizations and acid
and carbonyl (and possibly furan, pyran, and alkene) hydro-
genations require a catalyst to proceed.
9-15
*To whom correspondence should be addressed. Fax: 519-766-1499.
E-mail: mschlaf@uoguelph.ca.
(1) Mullen, C. A.; Boateng, A. A. Energy Fuels 2008, 22, 2104.
(2) Garcia-Perez, M.; Chaala, A.; Pakdel, H.; Kretschmer, D.; Roy,
C. Biomass Bioenergy 2007, 31, 222.
(3) Mohan, D.; Pittman, C. U.; Steele, P. H. Energy Fuels 2006, 20, 848.
(4) Hesse, W. Ullmanns Encyclopedia of Industrial Chemistry
;
Online Electronic Reference Work, 7th ed.; John Wiley and Sons: New
York, 2000.
(5) Karimi, E.; Gomez, A.; Kycia, S. W.; Schlaf, M. Energy Fuels
2010, 24, 2747.
(6) Yu, J.; Savage, P. E. Ind. Eng. Chem. Res. 1998, 37, 2.
(7) Trillo, J. M.; Munuera, G.; Criado, J. M. Catal. Rev.
;
Sci. Eng.
1972, 7, 51.
(8) Borowiak, M. A.; Jamroz, M. H.; Larsson, R. J. Mol. Catal. A:
Chem. 1999, 139, 97.
(9) Glinski, M.; Kijenski, J.; Jakubowski, A. Appl. Catal., A1995, 128,
209.
(10) Pestman, R.; van Duijne, A.; Pieterse, J. A. Z.; Ponec, V. J. Mol.
Catal. A: Chem. 1995, 103, 175.
(11) Pestman, R.; Koster, R. M.; Pieterse, J. A. Z.; Ponec, V. J. Catal.
1997, 168, 255.
(12) Pestman, R.; Koster, R. M.; Boellaard, E.; van der Kraan, A. M.;
Ponec, V. J. Catal. 1998, 174, 142.
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The corrosiveness, water content, and high polarity of bio-
oil makes the identification of a stable and promiscuous
catalyst for the reactions of Scheme 2 challenging. Commonly
usedcatalysts composedof a hydrogenating heavy metal (e.g.,
Re, Ru, Rh, Ir, Ni, Pd, and Pt) and a metal oxide support
(e.g., SiO
2
, Al
2
O
3
, ZnO, and TiO
2
) are susceptible to coking
and fouling of the catalyst surface by the highly polar sub-
strate and can, under the necessarily aqueous acidic condi-
tions, also suffer from the destruction of the support medium
andleachingof the toxic heavy metal intothe product, making
it either unusable or requiring further distillation prior to
combustion in a boiler, turbine, or piston engine.
Red mud is the waste byproduct of the Bayer process for
the refining of bauxite ore into pure Al
2
O
3
, the first step in the
production of aluminum metal. It consist of a highly alkaline
(pH14) mixture of Fe
2
O
3
, Al
2
O
3
, SiO
2
, TiO
2
, CaO, and Na
2
O
and is produced as an aqueous slurry on a very large scale
(>70 10
6
ton/year). At present, this nontoxic material is
routinely deposited in vast landfills. Alternative uses of red
mud are therefore of great economic and ecologic interest.
16
Red mud has previously been investigated as a catalyst
for the hydroliquefaction of biomass
17
and, at a higher
temperatures (800 C), for the production of hydrogen
frommethane
18
and a variety of other processes, notably coal
Scheme 1. Possible Reaction Sequences Leading to Resin Formation in Pyrolysis Bio-oil
Scheme 2. Fundamental Reactions Required for a Reductive Upgrading of Pyrolysis Bio-oil
5
(13) Das, J.; Parida, K. React. Kinet. Catal. Lett. 2000, 69, 223.
(14) Yokoyama, T.; Yamagata, N. Appl. Catal., A 2001, 221, 227.
(15) Deng, L.; Fu, Y.; Guo, Q. X. Energy Fuels 2009, 23, 564.
(16) http://www.redmud.org.
(17) Klopries, B.; Hodek, W.; Bandermann, F. Fuel 1990, 69, 448.
(18) Balakrishnan, M.; Batra, V. S.; Hargreaves, J. S. J.; Monaghan, A.;
Pulford, I. D.; Rico, J. L.; Sushil, S. Green Chem. 2009, 11, 42.
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liquefaction.
19
Recognizing that the composition of red mud
is essentially that of a very cheap
20
multifunctional acid/base,
hydrogenation, water-gas shift reaction (WGSR), and
Fischer-Tropsch catalyst (Fe
x
O
y
, TiO
2
, and SiO
2
) for the
reactions listed in Scheme 2,
19
we recently demonstrated its
use as a catalyst for the decomposition of formic and acetic
acids and mixtures thereof into ketones, alcohols, and hydro-
carbons at 350 C and hydrogen pressures ranging from 0 to
800 psi.
5
In this process, the red mud is reduced to a gray
magnetic, non-alkaline material [reduced red mud (RRM)]
that maintains its catalytic activity upon reuse. Also, because
of the elemental composition (Na, Ca, Al, Si, Ti, and Fe) of
red mud, any leaching of the catalyst into the upgraded
products is not of environmental concern, because they are
nontoxic and their oxides are ubiquitous in the bio- and
lithospheres. Here, we present the first study of the use of this
material as an upgrading catalyst for an actual bio-oil under
the same reaction conditions.
Experimental Section
General. An authentic operational sample of red mud was
supplied by Rio Tinto Alcans Jonquiere, Quebec operation.
RRMwas prepared as previously described.
5
Hemp-seed bio-oil
was supplied by the fast-pyrolysis plant of the Institute for
Chemicals and Fuels from Alternative Resources (ICFAR)
located at the University of Western Ontario, London, Ontario,
Canada.
21
Gas chromatography (GC) analysis was performed
on a Varian 3800 GCusing a 30 mDB-1701 column operating at
a constant flowrate of 1 mL/min. GC-mass spectrometry (MS)
analysis were performed either on a Varian Saturn 2000
GC-MS running in default electron ionization (EI) mode
(4 V axial bias and 1400 V multiplier) or at the Advanced Analysis
Centre of the University of Guelph (see the Supporting In-
formation). GC-MS fragmentation patterns of unknowns were
matched to National Institute of Standards and Technology
(NIST) 2005 and/or Saturn databases supplied with the instru-
ment. Water contents were determined by Karl Fischer titration
using a Metrohm 870 KF Titritino Plus titroprocessor. pH
values (relative to starting solutions) were determined by dilut-
ing the starting solutions as well as the polar and nonpolar
phases (1:9) with either water (polar/aqueous phase) or metha-
nol (nonpolar phase), respectively, and measuring the pH using
a Metrohm 827 pH lab glass electrode calibrated against
authentic buffer solutions (Metrohm 6.2307.110, pH 7 at 25 C
phosphate-based aqueous buffer solution). The pH values
cited are thus not directly equivalent to the aqueous scale but
refer to the relative acidities before and after upgrading in their
respective methanol sample solutions; i.e., they are only mean-
ingful in comparison to each other. Nuclear magnetic resonance
(NMR) analysis of liquid products was performed using a NMR
Bruker Cryoplatform 600 MHz. Nicolet 380 Fourier transform
infrared (FTIR) spectroscopy was used for infrared (IR) anal-
ysis (CaF
2
cells/plates).
Production of Hemp-Seed Bio-oil. All pyrolysis experiments
were carried out using a fluidized-bed pilot plant (Figure 1). The
heart of the plant was an atmospheric fluid-bed reactor, 0.078 m
in diameter, with a 0.52 m long cylindrical section, equipped
with an expanded section made up of a 0.065 m long trun-
cated cone with an upper diameter of 0.168 m, topped by a
second, 0.124 m long, cylindrical section. The total volume of
this configuration was 6.09 10
-3
m
3
, some of which was occu-
pied by the sand particles of the fluidized bed. This assembly
provided a nominal vapor residence time of 2 s (the nominal
vapor residence time was calculated by dividing the gaseous
volume of the reactor by the total nitrogen flowrate). Ahot filter
was installed at the gas exit. The fluidizing nitrogen was injected
through a perforated distributor plate at the base of the fluidized
bed, whichhad a static height of 0.15 m. Silica sand witha Sauter
mean diameter of 200 m was used to form the fluidized bed.
The reactor was equipped with 17 thermowells for temperature
measurements and control. A horizontal pulsating feeder was
used to inject ground hemp into the reactor at a height of 0.1 m
above the distributor plate.
22
This feeder ensured an excellent
and very rapid dispersion of the injected hemp seed into the
fluidized bed of hot sand particles. Band heaters on the outside
column wall, with a three-zone temperature controller, kept the
bed and freeboard at the specified temperature. Hemp seed,
when injected into the reactor, produced vapors that exited at
the top of the reactor through the hot filter section and flowed
into two condensers in series (one of which is shown in Figure 1).
Persistent aerosols were then separated in an electrostatic
demister. A more detailed description of the pilot plant and its
experimental procedures was previously provided.
23
The exact
yield of bio-oil was obtained fromthe mass of bio-oil collected in
the condensers and demister. The condensers and demister were
weighed before and after the experiment. Pyrolysis was carried
out at different temperatures and with a vapor residence time of
2 s. Each test was conducted with 300 g of hemp-seed powder.
The yields of bio-oil obtained varied between 45 and 60% (w/w)
per run. Fluidizing and carrier nitrogen volumetric flow rates
were adjusted tokeep the nominal vapor residence time constant
at all temperatures. The bio-oil was stored in a flame-proof
refrigerator at -4 C.
Upgrading Reactions. All reactions were carried out in a 300
mL Parr reactor (316 SS) fitted with a pressure dial, gold-coated
burst disk (p
max
= 5000 psi) and a vent valve. In a typical
experiment, bio-oil (25 g) and RRM (5 g) were mixed in the
stainless-steel autoclave. The unit was sealed, flushed, and
pressurized with hydrogen gas to 800 psi at ambient tempera-
ture. Reactions were stirred magnetically using a glass-coated
stir bar and brought to the reaction temperature of 350 C
(measured internally through a 316 SS thermocouple well) at a
Figure 1. Schematics of the ICFAR bubbling fluidized-bed pilot
plant.
(19) Sushil, S.; Batra, V. S. Appl. Catal., B 2008, 81, 64.
(20) Dependent upon geographical location, we estimate the cost of
red mud to a potential user to be equal or less to that of 1 ton of iron ore
(U.S. $100 at time of writing); i.e., the material might be available for
the cost of transportation by ship, barge, or railcar, allowing for
sacrificial use.
(21) http://www.eng.uwo.ca/icfar/.
(22) Berruti, F. M.; Ferrante, L.; Briens, C.; Berruti, F. Proceedings of
the Green Process Engineering Conference; Venice, Italy, 2009.
(23) Xu, R.; Ferrante, L.; Briens, C.; Berruti, F. J. Anal. Appl.
Pyrolysis 2009, 86, 58.
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heating rate of 3 C/min using an electric band heater. After 5 h, a
gas sample was taken from the headspace of the reactor and
analyzed by GC-MS. The reactor was cooled to ambient tem-
perature and opened, and its contents (products catalyst) were
removed and weighed. Fromthis mixture, bio-oil samples for GC,
GC-MS, IR, and NMR were prepared as described below with-
out catalyst separation, because this would influence the product
composition. To establish the fate of the catalyst, identical reac-
tions were carried out, in which the bio-oil products were ignored
and the catalyst solids were recovered by suspending the reaction
mixture in MeOH, filtration, washing with more MeOH, and
drying the remaining solids in an oven at 120 C overnight. The
recovered catalyst weight was 4.6-4.8 g; i.e., 92-96% of the
catalyst mass remains, with the mass loss being attributed to
the loss of chemically bound water and imperfect recovery of
solids during workup. The catalyst recovered by this procedure
maintains its catalytic activity in a repeat reaction.
Solvent Extraction. Atotal of 200 mg of oil decanted fromthe
product/catalyst mixture was dissolved in 3 mL of solvent of the
polarity series (water, methanol, acetone, acetonitrile, ethyl
acetate, diethyl ether, and n-hexane) and sonicated for 3 min.
The clear part of each sample was separated using a glass wool
column and subjected to analysis as described below.
NMR Sample Preparation. The extraction solvents used in
Solvent Extraction were removed in vacuo, and 100 mg of the
remaining bio-oil extract were dissolved in 1 mL of deuterated
chloroform for
1
H and
13
C NMR analyses (400 or 600 MHz).
GCSample Preparation. Atotal of 1 mLof methanol and0.5 mL
of each filtered solution produced by the method described in
Solvent Extraction were combined in 1.5 mL GC vials. GC traces
were obtained as described above using a 30 m DB-1701 column.
GC-MS Sample Preparation. Samples of 200 mg of oil de-
canted from the product/catalyst mixture were extracted with
3 mL of solvent of the polarity series (water, methanol, acetone,
acetonitrile, ethyl acetate, diethyether, and n-hexane), filtered
by a glass wool column. The solvent was removed in vacuo, and
the samples used for GC-MS analysis are as described in GC
Sample Preparation).
Chemical Class CompositionIdentificationUsingActivated Silica
Gel
24
. A total of 6 g of native bio-oil or product/catalyst mixture
was dissolved/suspended in 50 mL of n-pentane. The mixture was
stirred magnetically using a stir bar for 5 min and then separated
into two fractions as n-pentane-soluble and -insoluble compounds
(asphaltanes) by decantation. The n-pentane-insoluble part was
weighed after complete removal of n-pentane in vacuo. The weight
of this material is reported as asphaltane and, for the upgraded
bio-oil, includes 1.0gof recoveredcatalyst (6g/30g5g=1.0g),
i.e., overestimates the amount of insoluble organic material.
Table 1. Properties of Hemp-Seed Bio-oil before and after Upgrading
pH
a
water content (mg/mL)
entry reaction
b
W
oil after
(g) organic phase aqueous phase organic phase aqueous phase aqueous phase (g) (color)
1 crude oil n/a 6.4 n/a 40 n/a none
2 RRM catalyst
c
18.5 7.0 7.4 130 760 5.5 (pale yellow)
3 control 18.8 6.8 n/a 220 n/a none
a
Procedure: 1 g of reaction mixture and 9 g of water were shaken manually, then the mixture was sonicated for 15 min and stored at room temper-
ature for 24 h; also see the Experimental Section.
b
Reaction conditions: bio-oil (25 g) and RRM (5 g), 350 C, 800 psi H
2
(g) (cold); also see the
Experimental Section. Entry 1, bio-oil properties; entry 2, upgraded with RRM; entry 3, control reaction without catalyst.
c
Weight of re-isolated RRM
after reaction, 4.6-4.8 g.
Figure 2. Physical appearance of solvent extracts of hemp-seed bio-oil before and after upgrading.
(24) Acikgoz, C.; Kockar, O. M. J. Anal. Appl. Pyrolysis 2009, 85, 151.
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n-Pentane was also removed in vacuo from the soluble fractions,
andthe residue was separatedonactivatedsilica gel (70-230 mesh,
pretreated at 110 C for 2 h) using a 25 1 cm inner diameter
column. The column was eluted successively with 200 mL of
n-pentane, 200 mLof toluene, and 200 mLof methanol to produce
aliphatic (nonpolar), aromatic, and polar fractions, respectively.
The eluting solvent of each fraction was removed in vacuo, and the
fractions were weighed and subjected to other characterizations
and analyses by IR, NMR, and GC.
Phase Separation of the Oil Using Aqueous Salt Solution
25
.
Atotal of 6 g of a 30%(w/w) aqueous solution of K
2
CO
3
or CaCl
2
was added to 2 g of crude bio-oil or product/catalyst mixture.
The mixtures were shaken vigorously for 15 min and then
sonicated for 30 min. The resulting solutions were sealed and
stored at room temperature for 24 h, resulting in phase separa-
tion. The top phase consists of an aqueous salt solution extract
of the bio-oil or catalyst/bio-oil mixture. The bottom phase
consists of the heavy organic components plus recovered
catalyst. The two phases were separated by decantation and
weighed. The top phase was extracted with 3 40 mL of diethyl
ether. The top ether layer from this extraction contains the
heavy oxygenated components. It was dried over Na
2
SO
4
,
evaporated in vacuo at T<30 C, and weighed. The bottom
phase still contains the light oxygenated components, the weight
of which is indirectly determined by subtracting the directly
Table 2. Different Regions by the Proton Integration Percentage of Deuterated Chloroform
1
HNMRSpectra for Different Solvent Extractions of
Fresh Untreated and RRM-Upgraded Bio-oil after Removing the Extraction Solvents
parafinic (0-3 ppm) (%)
CHR(OH)
(3-5.5 ppm) (%)
olefinic/aromatic
(5.5-8 ppm) (%)
aldehyde/carboxylic acid
(8-12 ppm) (%)
extraction
solvent untreated
RRM
upgraded untreated RRM upgraded untreated RRM upgraded untreated RRM upgraded
methanol 88.15 95.60 5.98 0.31 5.77 4.05 0.11 0.08
acetone 91.30 94.02 5.10 1.28 0.92 4.70 2.68 0.00
acetonitrile 87.34 91.96 8.73 1.48 2.00 6.45 1.93 0.11
ethyl acetate 90.79 92.59 5.80 2.78 1.80 4.63 1.61 0.00
diethyl ether 88.39 94.05 6.92 1.93 2.76 4.03 1.93 0.00
Figure 3.
1
H NMR (CDCl
3
) spectra of methanol extraction for (top) untreated and (bottom) upgraded bio-oil.
(25) Song, Q.-H.; Nie, J.-Q.; Ren, M.-G.; Guo, Q.-X. Energy Fuels
2009, 23, 3307.
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weighed amounts of heavy oxygenated products (see above) and
hydrocarbons and tar (see below). The non-aqueous bottom
phase of the salt solution partition was treated with 3 40 mLof
methylene chloride. This mobilizes the tar components as a sus-
pendedsolid, allowing for separationfromthe completely insoluble
sedimented catalyst by decantation, and extracts the methylene-
chloride-soluble components into homogeneous solution. The ex-
pected mass fractions of catalyst (0.33 g) were recovered by this
procedure. Filtrationof the methylene chloride extracts gives asolid
consideredas tar (insoluble inmethylene chloride), whichwas dried
in vacuo at T<40 C and weighed. The filtrate was dried over
Na
2
SO
4
, filtered, and evaporated in vacuo at <40 C and contains
the soluble nonpolar hydrocarbons, which were weighed directly.
Thermogravimetric Analysis (TGA) of Untreated and Upgraded
Bio-oil. Four thermogravimetric tests were carried out to compare
the distillation behavior of the two fuel samples. Each sample
was taken from each fuel bottle after mechanical mixing. All tests
were carried out on a TA Instruments Q50 TGA under nitrogen
Figure 4.
13
C J-MOD NMR (CDCl
3
) spectra of methanol extraction for (top) untreated and (bottom) upgraded bio-oil (quartenary and CH
2
,
up; CH and CH
3
, down).
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atmosphere. The rate of the temperature increase was 10 C/min,
which is the same as several previous studies.
26-28
For each test,
a droplet of fuel was put inside an aluminum pad and then the
aluminum pad was placed over another platinum crucible and
heatedinside anelectric furnace witha controlledtemperature and
atmosphere. The temperature was increased linearly with time
from20 to600 Cover 58 min, andthe weight was recordedversus
temperature. Two tests were carried out for each fuel, and the
results were compared to diesel, which is a fully distillable fuel.
Results showed good repeatability.
Results
Nature and Characterization of Hemp-Seed Pyrolysis
Bio-oil and Conditions of Upgrading Reactions. The bio-oil
obtained by pyrolysis of industrial Ontario hemp seed
29
containing 30% (w/w) of triglycerides
30
in a bubbling
Figure 5. GC traces of hexane extractions: (top) retention time, 5-18 min; (bottom) retention time, 18-30 min for (1) untreated bio-oil and
(2) RRM-upgraded bio-oil (quantitatively identical injections using an auto-sampler robot).
(26) Lu, Q.; Yang, X.-l.; Zhu, X.-f. J. Anal. Appl. Pyrolysis 2008, 82,
191.
(27) Lapuerta, M.; Hernandez, J. J.; Rodr guez, J. Biomass Bioenergy
2004, 27, 385.
(28) Perez, M. G.; Lappas, P.; Hughes, P.; Dell, L.; Chaala, A.;
Kretschmer, D.; Roy, C. IFRF Combust. J. 2006, No. 200601.
(29) The industrial hemp and seed used contains none or only minute
traces of tetrahydrocannabinol (THC).
(30) Callaway, J. C. Euphytica 2004, 140, 65.
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Table 3. Compounds Identified by GC-MSFragmentation Patterns and M

Peaks in Acetone (A) and Hexane (H) Extracts of Hemp-Seed Bio-oil


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fluidized-bed pilot plant was selected for an initial assess-
ment of red mud as an upgrading catalyst, because it is more
easily handled than a more typical viscous bio-oil, as, e.g.,
obtained from corn stover or wood chips. It is an initially
free-flowing dark brown liquid and has a comparatively low
acidity. However, without upgrading, the oil still shows resin
formation and phase separation into an unusable material
when stored for >30 days at room temperature.
Upgrading reactions were carried out at 350 C (heating
rate, 3 C/min; total reaction time, 5 h) and 800 psi H
2
(g)
pressure (cold), i.e., the same conditions as establishedby our
previous study on red mud as a catalyst for the conversion of
Table 3. Continued
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HCOOH/HOAc. In these reactions, the red mud is reduced
to a gray magnetic material shown by powder X-ray diffrac-
tion (XRD) to contain Fe
3
O
4
and Fe metal.
5
The same
behavior is observed with the hemp oil rather than
HCOOH/HOAc as the substrate, but initial qualitative
screening of the phase-separated product mixtures of some
test reactions established that using gray RRM obtained by
the reaction with HCOOH/HOAc yielded almost neutral
(Table 1) as opposed to still strongly alkaline product phases
(pH > 9.5) obtained with native red mud. Given the limited
amount of bio-oil available to us at the time (1.5 Ltotal for
the whole study) and anticipated problems with strongly
alkaline product phases during the complex analysis se-
quences carried out on the products (see below), we therefore
limited this study to the RRM. Once reduced to RRM, the
catalyst does not change its appearance and can be reused
without the loss of activity; i.e., recycled RRM maintains its
magnetismand qualitatively yields the same phase-separated
Figure 6. IR spectra of (top) untreated and (bottom) organic phase of upgraded bio-oil (neat film, CaF
2
).
Figure 7. IR spectrum of the aqueous phase formed during upgrad-
ing bio-oil (neat film, CaF
2
cell).
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product distributions by the extractions and analyses de-
scribed below. The magnetism of the reduced catalyst may
also aid in its cost-effective recovery and separation fromthe
product mixture, if a larger scale process would ever be
implemented. Table 1 compares the pH and water content
by Karl Fischer titration of the crude oil, an upgraded
sample, and a control reaction without catalyst. The up-
graded oil separates into an oily organic phase and an
aqueous phase, both of which had a higher pH than the
crude oil. The control reaction did not generate an aqueous
phase but gave an intractable resin, which showed a sub-
stantial increase in water content caused by thermally induced
condensation reactions. The following sections describe more
detailed comparative analyses of crude versus upgraded bio-
oil by a variety of techniques.
Comparative Analysis of Crude versus Upgraded Bio-oil by
NMR, GC, GC-MS, and IR. The crude and upgraded bio-
oil were extracted with a series of solvents of increasing
polarity, comprising hexane, diethyl ether, ethyl acetate,
acetone, acetonitrile, methanol, and water. The physical
appearance and color comparison of these solvent extrac-
tions is shown in Figure 2. To determine the effect of
upgrading on the type and relative concentration of func-
tional groups in the bio-oil, the extraction solvents, diethyl
ether, ethyl acetate, acetone, acetonitrile, and methanol,
were removed in vacuo and the residue was dissolved in
CDCl
3
and analyzed by NMR. The relative percentages of
the
1
H NMR proton integrations of different peak regions,
i.e., paraffinic (0-3 ppm), CH-O (3-5.5 ppm), olefinic/
aromatic (5.5-8 ppm), and aldehyde/carboxylic acid (8-12
ppm), of bio-oil before and after upgrading for different
solvent extractions are listed in Table 2. In all cases, the
integration data reveal a substantial decrease in the relative
amounts of alcohols, aldehydes, and acids (i.e., polar and
reactive components) and increase in the relative amounts of
alkanes, alkenes, and aromatics (i.e., nonpolar components).
As an example, the
1
Hand
13
CNMRspectra of the methanol
extractions in CDCl
3
are shown in Figures 3 and 4. In
the MeOH extracts of the upgraded oil, almost no peaks
associated with the functional groups R-CH(OH)-R
0
,
R-(CdO)-R
0
, R-CHO, and R-COOH are present, in-
dicating that they have been converted into nonpolar
MeOH-insoluble products, i.e., alkanes and alkenes. Quali-
tative GC analysis of the various extracts mirrors the results
of the NMR study, with the GC traces of extracts obtained
from the upgraded oil and showing a substantially larger
number of peaks, i.e., volatile components. As an example,
Figure 5 compares the GCtraces of the hexane extracts of the
crude and upgraded oil using quantitatively identical injec-
tion conditions (auto-sampler robot) and flame ionization
detector (FID) response scales (0-12.5 mV). To identify and
compare the components of crude and upgraded oil, hexane
and acetone extractions were analyzed by GC-MS. The
identified components and their retention times are listed in
Table 3, with the upgraded oil again showing fewer oxygen-
ated compounds.
31
Both the crude and upgraded oils show
a large number of long alkyl chain molecules, free fatty acids,
or their esters, which are derived from the high triglyceride
content of the feedstock. GC-MS analysis of a gas sample
obtained from the headspace of the pressure reactor also
shows the presence of C3-C5 alkanes/alkenes, as well as
CO
2
generated from the ketonization or direct decarboxyla-
tion of carboxylic acids present. The maximum pressure
observed during the RRM-catalyzed reaction was 2200 psi,
while the control reaction in the absence of RRM resulted in
the lower maximum pressure of 1800 psi (entry 3 in Table 1).
The GC-MS of a gas-phase sample of the control was
essentially identical to that of the RRM reaction, but as stated
above, no aqueous phase was generated and the product was
an intractable resin that was therefore not further analyzed.
Figure 6 compares the IR spectra (neat, CaF
2
cell) of the
crude oil to that of the oily organic phase obtained from the
upgrade reaction (entry 2 in Table 1). The upgraded fraction
Figure 8.
1
H NMR (DMSO-d
6
) spectrum of the aqueous phase formed during upgrading of bio-oil.
Table 4. Chemical Class Composition Identification of Untreated and
Upgraded Bio-oil by Chromatographic Fractionation on an Activated
Silica-Gel Column Using n-Pentane, Toluene, and Methanol as
Consecutive Eluents
weight fraction analysis
bio-oil
asphaltane
(%)
nonpolar
hydrocarbons
(%)
polar
hydrocarbons
(%)
aromatics
(%)
untreated 50.0 11.7 21.7 16.6
RRM
upgraded
11.7 53.3 10.0 25.0
(31) See the Supporting Information for actual GC-MS spectra and
detailed analysis conditions.
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does not show the large
OH
and
CO
peaks present in the
crude oil but well-defined
C-H
and
CdC
bands, again
indicating that any alcohol, aldehyde, ketone, andcarboxylic
functions had been converted to alkanes, alkenes, and aro-
matic compounds. Figure 7 shows the IR of the correspond-
ing aqueous phase, and Figure 8 shows the corresponding
1
H NMR spectrum. Both spectra are dominated by water
(75% by KF titration) and show only small amounts of
unidentified organics.
Comparative Stability Analysis of Crude versus Upgraded
Bio-oil by Solvent Extraction and Salt Solution Partition.
An important criterion for the effectiveness of the bio-oil-
upgradingreactionis the relative stabilityof the organic product
fraction against further condensation and resin formation and
the total amount of insoluble asphaltanes/tar present in the oil.
To determine more quantitatively the effect of the upgrading
reaction on these two parameters, starting 30 days after receipt
of the bio-oil, we carried out a larger scale solvent extraction
study following the protocol developed by Acikgoz and
Kockar,
24
which separates the oil into the four different chemi-
cal classes, asphaltane, nonpolar hydrocarbon, polar hydro-
carbon, and aromatics, according to their relative (in)solubility
in n-pentane, toluene, and MeOH and a salt solution parti-
tion into hydrocarbons, heavy and light oxygenates, and tar
(equivalent to asphaltanes), followed by solvent extraction of
the phases obtained by extraction with diethyl ether and
methylene chloride following the protocol developed
by Song and co-workers.
25
In both cases, the relative
amounts of the fractions obtained were determined gravi-
metrically, as described in detail in the Experimental Section.
Table 5. Summary of Results of Aqueous Salt Extraction of Untreated and Upgraded Bio-oil
salt untreated upgraded
K
2
CO
3
(aqueous,
30 wt %)
upper layer (heavy and
light oxygenated) (%)
bottom layer (tar and
hydrocarbons) (%)
upper layer (heavy and
light oxygenated) (%)
bottom layer (tar and
hydrocarbons) (%)
48.5 51.5 4.9 95.1
heavy oxygenated
(%)
light
oxygenated (%)
tar (%) hydrocarbons
(%)
heavy oxygenated
(%)
light
oxygenated (%)
tar (%) hydrocarbons
(%)
35.5 13 30 21.5 3 1.9 14.0 81.1
K
2
CO
3
(aqueous,
30 wt %)
(after 60 days)
upper layer (heavy and
light oxygenated) (%)
bottom layer (tar and
hydrocarbons) (%)
upper layer (heavy and
light oxygenated) (%)
bottom layer (tar and
hydrocarbons) (%)
60 40 5.1 94.9
heavy oxygenated
(%)
light
oxygenated (%)
tar (%) hydrocarbons
(%)
heavy oxygenated
(%)
light
oxygenated (%)
tar (%) hydrocarbons
(%)
55 5 40 0 3.4 1.7 14.0 80.9
CaCl
2
(aqueous,
30 wt %)
upper layer (heavy and
light oxygenated) (%)
bottom layer (tar and
hydrocarbon) (%)
upper layer (heavy and
light oxygenated) (%)
bottom layer (tar and
hydrocarbon) (%)
55 45 6 94
heavy oxygenated
(%)
light
oxygenated (%)
tar (%) hydrocarbons
(%)
heavy oxygenated
(%)
light
oxygenated (%)
tar (%) hydrocarbons
(%)
43 12 33 12 4.2 1.8 17 77
Figure 9. Effect of RRM-catalyzed upgrading of bio-oil on the amount of polar and nonpolar hydrocarbons, aromatics, and asphaltane
components of the oil, as determined by chemical class separation through chromatographic fractionation on an activated silica-gel column
using n-pentane, toluene, and methanol as consecutive eluents.
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Tables 4 and 5 give the results of these studies in numerical
format. The fractions obtained by either protocol consistently
show substantially reduced amounts of asphaltanes/tar and
oxygenated components and a substantially increased amount
of nonpolar hydrocarbons and aromatics (Figures 9 and 11).
To compare the relative stability of the upgraded versus
crude, bio-oil samples of both aged for 30, 60, and 90 days
were reanalyzed by the solvent extractionprotocol. Figure 10
shows that the fraction distribution in the upgraded oil
remains essentially unchanged, while the amount of insolu-
ble asphaltane increases to 90% (w/w) in the crude oil,
which is accompanied by a visually apparent increasing
resinification of the material. A similar trend is observed
when reanalyzing the oil after 30 and 60 days using the salt
solution partition protocol (Figure 12). Notably, with both
methods, the amount of recoverable nonpolar hydrocarbons
drops to 0% (w/w) after 60 and 90 days, respectively.
32
Comparative Analysis of Crude versus Upgraded Bio-oil by
TGA. An ideal upgrading result would be the conversion of
bio-oil into a fully distillable fuel meeting an American
Society for Testing and Materials (ASTM) or similar stan-
dard. This can most easily be evaluated by carrying out a
TGA in comparison to a fuel that meets this criterion. We
therefore subjected the crude and upgraded oils to TGA and
compared them to a commercial diesel oil sample that meets
the CAN/CGSB-3.517 automotive low-sulfur diesel fuel
standard. Figures 13 and 14 and Table 6 give the results of
the TGA experiments. The TGA curve can be divided into
three regions according to temperature. The first region is
vaporization of the light components. As can be seen in
Figure 13, at temperatures lower than 300 C, most of
the light components of the fuels vaporize. The upgraded
fuel has more volatiles because its TGA curve is lower until
250 C. Between 200 and 300 C, the crude oil shows a peak
in the weight derivative shown in Figure 14; i.e., the crude oil
seems to have more components boiling off, as shown in
weight derivative, which we attribute to a thermally induced
formation of water through condensation reactions, which
Figure 10. Evaluation of the relative stability of crude and upgraded bio-oil fractions obtained by chemical class separation through
chromatographic fractionation on an activated silica-gel column by measuring the relative amounts of tar and polar and less polar
hydrocarbons at 30, 60, and 90 days: (left) untreated and (right) upgraded.
Figure 11. Effect of RRM-catalyzed upgrading of bio-oil on the amount of polar and nonpolar hydrocarbons, aromatics, and asphaltane
components of the oil, as determined by chemical class separation by salt solution extraction (values shown are the averages of the CaCl
2
and
K
2
CO
3
extractions shown in Table 5).
(32) The 60 day result for the salt partition protocol promoted us not
to attempt an extraction after 90 days.
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Figure 12. Evaluation of the relative stability of crude and upgraded bio-oil fractions obtained by chemical class separation by salt solution
extraction (K
2
CO
3
; see Table 5) by measuring the relative amounts of tar and polar and less polar hydrocarbons at 30 and 60 days: (left)
untreated and (right) upgraded.
Figure 13. TGA curve for two bio-oil samples and diesel.
Figure 14. Derivative of the TGA curve (DTGA) for two bio-oil samples and diesel.
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are no longer possible in the upgraded fuel. Asecond smaller
peak in the weight derivative of the original fuel occurs
between 300 and 400 Cand at 400-500 Cfor the upgraded
fuel. This change of behavior could be attributed to the
polymerization of alkenes present inthe upgradedfuel versus
pyrolysis of heavy fractions in the untreated fuel in the range
of 300-500 C, as previously observed by others.
27,28
Discussion
The sum of the analytical results obtained suggests that, at
350 C and 800 psi hydrogen pressure, RRM is in fact acting
as an effective catalyst for the upgrading of the hemp-seed
pyrolysis bio-oil by a set of deoxygenation reactions that are
consistent withor at least comprise those laid out in Scheme 2.
Phase separation of an aqueous phase [75% (w/w) water
and25%(w/w) oxygenatedorganics byKarl Fischer titration]
and generation of CO
2
lead to substantial mass loss (30%,
w/w), yielding 70% (w/w) of an organic product phase that
is primarily composed of non-oxygenated, more volatile and
less reactive hydrocarbons that, as a consequence of the nature
of the feedstock used, appear primarily derived from long-
chainfatty acids. The stabilityof the upgradedoil against resin
formation also points to a much reduced concentration of
reactive oxygen-based functional groups, allowing for its
storage for extended periods of time. While not evaluated
here (because of the limited amount of material available),
both of these factors should result in a higher energy density
and better burn characteristics of the oil. The TGAshows that
the upgrading did not result in a highly desirable fully distil-
lable fuel but did increase the concentration of the lighter
components of the fuel. However, it also increased polymer-
ization and, therefore, the amount of solid residue formed at
600 C. Onthe basis of the
1
HNMRandGC/GC-MS results
discussed above (Tables 2 and 3), this is caused by a higher
concentration of polymerizable alkene components in the
upgraded oil, which, because of their fatty-acid-derived long
chains, are relatively difficult to completely hydrogenate on
the heterogeneous iron catalyst.
Conclusion and Outlook
RRM, obtained by the reaction of mining waste red mud
with HOAc/HCOOH, is a nontoxic and extremely cheap
catalyst for the upgrading of pyrolysis bio-oils that, with an
external supply of reducing equivalents in the form of hydro-
gen gas, achieves a substantial reduction of the concentration
of oxygen-based functional groups in the oil by generating
water and CO
2
as the oxygen-carrying byproducts, effectively
lowering the overall oxygen content of the oil and rendering it
stable against resin formation.
Future studies will focus onthe use of red-mud-basedcatalysts
onmore typical andhighlyacidic bio-oils, as obtainedfrommore
common agri- and silvi-cultural byproducts, such as wheat
straw, corn stover, and wood or bark chips. With a higher
HCOOH content, these feedstocks should allow for an effective
direct use of red mud with the in situ generationof hydrogen and
the gray RRM employed in this study.
5
A further intriguing
possibility under consideration by the authors is the use of red
mud as the bed material in a fluidized-bed reactor used to
produce the oil, which may effectively lead to a simultaneous
bio-oil production and upgrading process directly yielding a low
acid and low oxygen content bio-oil. The low cost and high
availability of the catalyst also suggests that a co-processing of
biomass/red mud with a continuous feed-through of both the
carbon- andmetal-oxide-basedfeedstocks maybe viable, leading
toasimultaneous value additiontoboththe biomass andmining
wastes used; i.e., in addition to the upgraded bio-oil, large
amounts of a non-alkaline magnetic material similar to the
RRM employed here could be obtained. Because of its higher
iron content by weight, it may find direct use as an iron ore or
become a component of aluminoferrite belite cement.
33
Acknowledgment. The authors thankDrs. Guy Forte and Guy
Peloquin, Rio Tinto Alcan (Jonquiere, Quebec Operation), for
supplying an authentic operational process sample of redmud, Dr.
Dyanne Brewer of the Advanced Analysis Centre (AAC) at the
University of Guelph for assistance with the mass spectrometric
analysis, and the Agricultural Biorefinery Innovation Network
(ABIN) as funded by Agriculture and Food Canada as well as
FPInnovations Canada for supporting this research.
Supporting Information Available: Detailed analysis of the
composition of red mud by X-ray fluorescence (XRF; Rio Tinto
Alcan) and details of the GC-MS analysis of the compounds
listed in Table 3. This material is available free of charge via the
Internet at http://pubs.acs.org.
Table 6. TGA Residue Weight for All Cases
sample identification
a
residue after
600 C (%)
initial weight of the
fuel drop (mg)
untreated (I) 6.51 20.5
untreated (II) 8.13 10.67
upgraded (I) 12.32 12.12
upgraded (II) 11.35 24.44
a
Corresponds to the sample identification in Figure 13.
(33) Vangelatos, I.; Pontikes, Y.; Angelopoulos, G. N. Proceedings of
the International Ceramic, Glass, Porcelain Enamel, Glaze and Pigment
Congress; Eskis-ehir, Turkey, 2009.

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