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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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Energy Fuels 2010, 24, 65866600
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DOI:10.1021/ef101154d Karimi et al.
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.
6588
Energy Fuels 2010, 24, 65866600
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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