ARTICLE

pubs.acs.org/IECR

Catalytic Thermochemical Conversion of Glycerol to Simple and

Polyhydric Alcohols Using Raney Nickel Catalyst
Randy L. Maglinao and B. Brian He*
Biological and Agricultural Engineering, University of Idaho, Moscow, Idaho 83844, United States
ABSTRACT: The crude glycerol from biodiesel production possesses low economic values and alternative ways of converting it to
valuable chemicals are needed to sustain the biodiesel industry. This study aimed to investigate the production of primary alcohols
and propylene glycol from glycerol through a catalytic thermochemical process without an external supply of hydrogen. The eects
of reaction time, water to glycerol ratio, and doses of catalyst on glycerol conversion and alcohol yields were investigated using a
batch pressure reactor and Raney nickel catalyst. The presence of alcohols and gases in the products conrmed that hydrogen was
produced and was utilized in the formation of propylene glycol through hydrogenolysis. Ethanol and propylene glycol yields of up to
10.4 ( 0.2 and 33.2 ( 1.4 mol %, respectively, were observed. It was also concluded that ethanol is formed through hydrogenolysis
of propylene glycol and its yield improves at extended reaction time and increased initial water content of the feed.

INTRODUCTION
Biodiesel is an alternative fuel produced by transesterication
of an alcohol and a plant oil or animal fat. With the introduction of
the next generation feedstocks such as jatropha and algae, it is
predicted that the biodiesel production will be tripled by 2020.1
However, along with the success of the biodiesel industry, the global
production of glycerol, a byproduct of biodiesel production, also
increased. The rapid increase in crude glycerol greatly aected the
market price of glycerol, which dropped from $0.43/kg in 2003 to
$0.18/kg in 2010 for pure glycerol, and to only $0.02/kg for crude
glycerol.2,3 Although various products can be derived from glycerol
for dierent applications, the demand for these products is still not
enough to handle the increasing supply of crude glycerol. Thus, new
technologies of producing valuable products with relatively large
markets from glycerol are urgently needed.
Converting glycerol to primary alcohols such as ethanol and
methanol, and polyhydric alcohols such as propylene glycol, through
a thermochemical process is a potential way to increase the value of
crude glycerol. Thermochemical processes can use heat only to
break down organic matter into desired products. The problem with
thermochemical processes is, however, the low selectivity toward
desired products. Conventional thermochemical conversions involve high operating temperatures. Such conditions also favor
further decomposition and repolymerization of the desired products
to undesired compounds such as char and tar. This problem can
be avoided if appropriate catalysts are employed to increase the
selectivity and eciency of the chemical process. Catalysts have the
capability to decrease the energy required by lowering the activation energy of a chemical reaction and to increase the selectivity
by breaking specic chemical bonds to produce the intended
products. It is logical, therefore, to apply catalysts to the thermochemical decomposition of glycerol to improve the selectivity
toward the desired alcohol products.
Metal catalysts have been used in converting glycerol to
polyhydric alcohols and hydrogen through hydrogenolysis and
reforming, respectively. Ethylene glycol and propylene glycol are
examples of useful polyhydric alcohols that can be derived from
r 2011 American Chemical Society

glycerol using metal catalysts. However, the production of propylene glycol from glycerol has received more attention and is mostly
researched as compared to the production of other polyhydric
alcohols such as 1,3-propanediol and ethylene glycol.4
8 Propylene
glycol is also the preferred product rather than ethylene glycol
because of the less desired toxic characteristics of ethylene glycol.
Suppes and co-workers performed research on the conversion of
glycerol to propylene glycol and patented a process of selectively
producing propylene glycol.9
11 In producing propylene glycol, one
of the primary hydroxyl groups in glycerol is selectively removed
through hydrogenolysis using a metal catalyst. There are two
theories in hydroxyl group selective removal, namely, the acetol
pathway and the glyceraldehyde pathway,4 of which the acetol
pathway has been the most widely investigated. According to the
theory of acetol pathway, the secondary hydroxyl group of glycerol is
dehydrated to acetol followed by catalytic hydrogenation to propylene glycol. Therefore, hydrogen presence in the system is a must.
In addition to polyhydric alcohols, ethanol and methanol are
other valuable products that can be derived from glycerol. In
producing propylene glycol from glycerol, degradation of acetol
and propylene glycol to other products has been reported.10
However, secondary reactions such as the decomposition of acetol
and propylene glycol can be utilized in a favorable way to produce
valuable compounds in addition to propylene glycol. Wojcik and
Adkins12 used hydrogenolysis to prepare specic hydrocarbons
from long-chain alcohols. In their process, the carbon with the
hydroxyl group is cleaved at the carbon to carbon bond from the
long-chain alcohol, producing a hydrocarbon, methane, and water.
Based on this concept, further hydrogenolysis of acetol could lead to
ethanol formation, as shown in Scheme 1.
Theoretically, hydrothermal cracking of glycerol, i.e., the hightemperature reaction of glycerol with water, can produce
Received: December 28, 2010
Accepted: March 31, 2011
Revised:
March 30, 2011
Published: March 31, 2011
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Scheme 1. Hydrogenolysis of Acetol to Ethanol

methanol. The advantage of co-producing these low boiling

point alcohols along with propylene glycol is that they can be
easily separated through distillation. Still, to produce these
alcohols from glycerol through this pathway, hydrogen is needed.
Hydrogen is essential for hydrogenolysis of glycerol to occur,
but it can come from the reactant itself. Studies have reported
successful production of hydrogen from glycerol.13
16 Several
processes have been employed to convert glycerol to hydrogen,
including steam reforming, autothermal reforming, and aqueousphase reforming.17
19 Steam reforming uses steam to react with an
organic compound to produce carbon dioxide and hydrogen.20
23
Autothermal reforming is the combination of steam reforming and
oxidation of glycerol.18 This is achieved by preheating a glycerol/
water mixture at 300 ( 10 C and feeding the vaporized mixture
with lean air to a reactor with a catalyst.18 The heat produced by the
oxidation of glycerol is used by the steam reforming reactions to
produce hydrogen, and such a system reduces the overall energy
requirement of the process. The above-mentioned processes are
typically operated at temperatures over 400 C at atmospheric
pressure. On the other hand, aqueous-phase reforming operates at
higher pressures (2.5 MPa) but at relatively lower temperatures
(220 C).19,24 These conditions are similar to those required for
the hydrogenolysis of glycerol to propylene glycol. If hydrogen can
be produced from glycerol at conditions where hydrogenolysis
occurs, it can be hypothesized that glycerol can undergo hydrogenolysis to catalytically produce valuable primary and polyhydric
alcohols without external hydrogen supply, which is an ideal process
with signicant economic advantages.
Currently, there is no in-depth investigation reported on
converting glycerol to alcohols using a catalytic thermochemical
process without external hydrogen supply. This study aimed to
investigate the production of primary alcohols and propylene
glycol through catalytic thermochemical process with no external
hydrogen supply and to determine the favorable conditions for
maximizing the same.

METHODS
Materials and Equipment. Reagent grade glycerol (BDH
distributed by VWR, West Chester, PA) with 99.5% purity was
used throughout the experiments in our first phase research to
avoid the interference of impurities found in crude glycerol from
biodiesel. Active Raney nickel catalyst was purchased from
Sigma-Aldrich (St. Louis, MO) and used. Standards of methanol,
ethanol, n-propanol, 2-propanol, propylene glycol, acetol, and
glycerol were prepared for calibrating the gas chromatograph.
Methanol (99.8% purity), acetone (99.7%), and 2-propanol
(99.99%) were purchased from EMD (Gibbstown, NJ). Acetol
(95%) and propylene glycol (99.5%) was purchased from Alfa
Aesar (Ward Hill, MA), and 1-propanol (99.9%, J.T. Baker) was
purchased from VWR (West Chester, PA). Ethanol was bought
from AAPER, Alcohol and Chem. Co. (Shelbyville, KY). Diethel
ether (99.0%, BDH) was purchased from VWR.

Figure 1. Schematic diagram of the reactor system used in the study.

A 300 mL pressure reactor from Parr Instruments (Moline, IL)

was used for conducting the experiments in this study. The reactor is
capable of handling up to 20 MPa (3000 psig) of pressure and
350 C of temperature. The reactor is equipped with a controller to
regulate and monitor the operating temperature, pressure, and
agitation motor speed. A capture vessel (a vacuum ask) was
installed along the exhaust line to capture any condensables escaping
during removal of gases after reaction (Figure 1).
Analysis of Samples. An Agilent 6890N gas chromatograph
with a flame ionization detector (FID) was used for analyzing the
primary and polyhydric alcohols and residual glycerol. For this
purpose, the column was a 30 m by 0.32 mm inside diameter DBwax column with 0.5 m film thickness. A 5 g amount of the sample
and 100 mg of the internal standard (diethyl ether) were mixed and
deionized water was added to make up 10 mL of solution. The
solution was then diluted by adding HPLC grade acetone to the
solution to make up 50 mL of the final solution. The oven
temperature was programmed to begin at 30 C for 10 min before
ramping to 220 C at 30 C/min with a final hold time of 13 min.
Samples of 1 L were injected with a split ratio of 60:1 and with an
inlet port temperature of 250 C. The inlet port temperature was set
slightly lower than 290 C to prevent any glycerol decomposition.
Slight and complete decomposition below its boiling point have
been reported.25,26 Helium was used as the carrier gas with its
pressure programmed to start at 48 kPa (7 psig) with a holding time
of 10 min and then ramped to 103 kPa (15 psig) at 34.5 kPa/min (5
psi/min) to increase the flow rate of glycerol. The FID was set at
300 C with a nitrogen makeup gas of 30 mL/min.
Experimental Procedures. Experiments of catalytic thermochemical conversion of glycerol to alcohols were conducted using
the batch reactor as described in Figure 1. Glycerol, water, and the
metal catalyst were mixed in the reactor. Nitrogen gas was used to
purge the headspace of the reactor for 1 min to remove oxygen. The
reactor was then heated to 230 C and maintained at the set reaction
time. Upon the completion of the reaction, the reactor was cooled to
room temperature by the equipped cooling mechanism. The
noncondensable gases formed during the reaction were removed
through the exhaust valve and vented out. The final weight of the
liquid product and catalyst was determined by measuring the reactor
with the product (liquid and catalyst) and taking the difference of
the premeasured weight of the empty reactor. The liquid product
collected from the reactor was separated from the catalysts using a
vacuum filtration at constant vacuum pressure of 16.9 kPa (5 in.Hg).
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Table 1. Conversion Rates of Glycerol and Yields of Gases at 230 C Using Raney Nickel Catalysta
reaction time (min)

a
c

WGMRb

rate of conversion (mol %)

pressure di c (MPa)

yield of gas (mol %)

15

1:1

91.1 ( 2.3

2.314 ( 0.158

13.1 ( 1.7

45

1:1

98.6 ( 0.2

3.240 ( 0.137

18.2 ( 0.7

75

1:1

99.6 ( 0.5

4.904 ( 0.458

30.9 ( 3.9

105

1:1

99.9 ( 0.1

5.216 ( 0.123

33.9 ( 0.2

45

7:3

99.9 ( 0.1

3.493 ( 0.258

35.5 ( 2.8

45

3:7

95.3 ( 0.2

2.893 ( 0.042

12.3 ( 0.3

Each treatment was conducted in triplicate. Data are presented as average ( standard deviation. b WGMR = water to glycerol mass ratio in the feed.
Measured at 30 C before and after the reaction.

8.314 m3 Pa/(mol/K); and Ao, Bo, Co, Do, Eo, a, b, c, d, R, , and

are intermediate parameters.
The experimental data were processed and analyzed according
to the following denitions:
ni;gly
nf ;gly
 100
glycerol conversion rate=mol %
ni;gly
where ni,gly is the moles of glycerol before the reaction (initial
quantity) and nf,gly is the moles of glycerol after the reaction
(residual quantity).
nj;p
 100
yield of alcohol j=mol %
ni;gly

Figure 2. Alcohol yields versus reaction time. Each treatment was

conducted in triplicate, and the error bars represent the standard
deviations. The symbols in the plot are as follows: 9, propylene glycol;
2, ethanol; b, acetol.

Whatman Qualitative No. 2 filter paper (8 m pore size) was used

throughout the study.
The amount of gas evolved was estimated using the modied
Benedict
Webb
Rubin gas equation for real gas mixtures
(eq 1). The intermediate parameters were evaluated on the basis
of the critical parameters such as temperature, density, and
acentric factor of its pure species as described by Starling and
Han.27 The dierence in the pressure of the reactor before and
after the reaction at the same temperature, specically at 30 C,
was assumed to represent the contribution of gas formed. Thus,
this pressure dierence was used in the gas equation. Also, it was
assumed that carbon dioxide was the dominant gas formed due to
the inability to determine the composition of the gaseous
products in this study.
Benedict
Webb
Rubin equation of state:


Co Do Eo
P FRT Bo RT
Ao
2 3
4 F2
T
T
T




d 3
d 6
bRT
a

F R a
F
T
T

cF3
F2 exp
F2
T2

where P is the absolute pressure, Pa; T is the absolute temperature, K; F is the gas density, mol/m3; R is the gas constant,

where nj,p is the moles of compound j in the product and

j = methanol, ethanol, or propylene glycol.
ngas
yield of gases=mol %
 100
nc;feed
where ngas is the moles of gases formed and nc,feed is the moles of
initial carbon in the feed.

EXPERIMENTAL RESULTS
Effect of Reaction Time. Table 1 summarizes the experimental results of the overall glycerol conversion and gaseous
products at different reaction time and water to glycerol mass
ratio. Water to glycerol mass ratio, WGMR, is defined as the ratio
of water and glycerol used in the feed. It shows that at 45 min and
longer into the reaction, more than 98 mol % glycerol was
converted (Table 1). In addition to liquid products, gaseous
compounds were also formed during the reaction. The results
also show that more gaseous compounds were formed at
extended reaction time. Pairwise analysis on the pressure readings using the least significant difference test (LSD test) at 95%
confidence level by the Statistical Analysis System software (SAS
Institute Inc., Cary, NC) suggested that there were significant
differences in the amount of gases formed from 15 to 75 min
while no differences were observed thereafter.
Propylene glycol and ethanol were the major liquid products
of the process. Other simple alcohols, such as methanol and
2-propanol, were also produced but in small amounts. Acetol,
which is the proposed intermediate compound for producing
propylene glycol and ethanol, was also present in the liquid
product. The alcohol yields against the reaction time are shown
in Figure 2. Ethanol yield increased from 6.1 ( 0.4 to 10.4 ( 0.2
mol % while propylene glycol decreased from 30.2 ( 0.7 to 17.4 (
0.7 mol %. Similarly to that of propylene glycol, the yield of acetol
dropped at extended reaction time.
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Table 2. Alcohol Yields at Dierent Water to Glycerol Mass

Ratiosa
for given water to glycerol mass ratio
alcohols

7:3

1:1

3:7

methanol

3.919 ( 0.645

2.658 ( 0.463

2.115 ( 0.125

2-propanol

0.149 ( 0.024

0.547 ( 0.425

0.065 ( 0.006

ethanol
n-propanol

10.911 ( 0.387
0.456 ( 0.012

8.519 ( 0.733
0.388 ( 0.028

7.249 ( 0.326
0.380 ( 0.012

Each treatment was conducted in triplicate. Data are presented as

average ( standard deviation.

Figure 4. Alcohol yields of at dierent doses of nickel catalyst. The

symbols in the plot are as follows: 9, propylene glycol; 2, ethanol; b,
acetol.

Figure 3. Alcohol yields at dierent initial amounts of water in the feed.

Each treatment was conducted in triplicate, and the error bars represent
the standard deviations. The symbols in the plot are as follows: 9,
propylene glycol; 2, ethanol; b, acetol.

Effect of the Initial Amount of Water. Water is an essential

ingredient in producing hydrogen from glycerol through the watergas shift reaction. Thermodynamic analysis on steam reforming of
glycerol showed that more hydrogen can be produced at higher
water to glycerol mass ratios.20,21 For example, Luo et al.19 obtained
higher hydrogen yields at 5 wt % glycerol than that at 10 wt % in
water solutions at 220 C. In addition, water also helps maintain a
homogeneous temperature profile throughout the liquid-phase
reaction and inhibits chemical dehydration of glycerol to unwanted
intermediates and products in hydrogenolysis.10 Table 2 summarizes the yields of primary alcohols at different water to glycerol
mass ratios. The ethanol yield increased as the water content in the
solution increases. A similar trend was observed for methanol and
gaseous products. On the other hand, less propylene glycol was
produced at higher water to glycerol mass ratios (Figure 3).
Comparing the cases of 7:3 and 1:1 of water to glycerol mass ratios,
the decreasing trend of propylene glycol can be attributed to the
production of more gaseous compounds as manifested by the
increasing operating pressures (Table 1). However, this trend does
not hold when the initial amount of water was further decreased. As
shown in Figure 3, propylene glycol peaked near the water to
glycerol mass ratio of 1:1 but the amount of gaseous products still
kept decreasing as shown in Table 1.
Effect of Catalyst. Figure 4 summarizes the yield trends of
alcohols at different amounts of nickel catalysts at 230 C for 45 min
of reaction and 1:1 water to glycerol mass ratio. Increasing the doses
of the catalysts resulted in the increases of the yields of both ethanol

and propylene glycol. The yield of propylene glycol followed a

quadratic path and reached its peak at 6.4 wt % nickel catalyst.
The decrease in the alcohol yields from using 6.4
8.9 wt %
suggest that increasing the concentration of nickel catalyst to
above 6.4 wt % would not signicantly improve the yields of
propylene glycol and ethanol under the studied conditions. The
overall conversion of glycerol and formation of gases were also
aected by the dosage of catalyst applied. The glycerol conversion rate increased from 49.04 to 98.59 mol % and the gas yields
increased from 3.69 to 17.60 mol % when increased concentrations of nickel catalyst were applied (Table 3).

DISCUSSION
The presence of signicant amounts of ethanol and propylene
glycol in the liquid product conrms that hydrogenolysis had
occurred in the catalytic thermochemical conversion of glycerol.
The formation of gaseous products also supported the authors
hypothesis that a portion of glycerol has been converted to
hydrogen and utilized simultaneously in the production of alcohols.
Although the presence of hydrogen was unconrmed due to a lack
of tests for this study, we have no other explanation for the formation
of gases other than the aqueous-phase reformation of glycerol that
occurs at the same conditions as in this study, which typically
produces carbon dioxide and hydrogen.24 Methanol and n-propanol
were also produced in the process. The low yields of methanol and
n-propanol, however, suggest that the conditions explored in the
study favor other competing reactions such as formation of
propylene glycol.
Effect of Operating Parameters. The yield of propylene glycol
was significantly affected by the parameters tested in this study. At
230 C, the highest yield of propylene glycol was observed at the
shortest reaction time, i.e., 15 min. Extending the reaction time
resulted in degradation of propylene glycol to other products as
indicated by the increasing yields of ethanol and gases (Table 1 and
Figure 2). Maris and Davis6 also observed a decreasing trend in
propylene glycol yields when the reaction time was prolonged. In
their study, the yield of propylene glycol peaked at the same time
when almost all of the glycerol has been converted to products and
then the yield continuously decreased thereafter. Although it took
100 min of reaction to achieve a conversion rate of glycerol greater
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Table 3. Conversion Rates of Glycerol and Gas Yields at 230 C for 45 min and 1:1 Water to Glycerol Mass Ratio Using Raney
Nickel Catalyst
catalyst concentration

glycerol conversion

yield of gas

catalyst concentration

glycerol conversion

yield of gas

(wt %)

rate (mol %)

(mol %)

(wt %)

rate (mol %)

(mol %)

1.0
2.9

49.04
77.19

3.69
8.31

6.4
8.9

95.75
98.59

16.36
17.60

4.7

87.95

12.12

Scheme 2. Hydrogenolysis of Propylene Glycol to Ethanol

than 90 mol % in the study of Maris and Davis, almost all glycerol
has been converted to products after 45 min in our study, as
summarized in Table 1. Comparing it to the results from the study of
Maris and Davis,6 it can be concluded that the production of
propylene glycol had reached its maximum at or earlier than 15 min.
The degradation of propylene can also be explained by the increase
of gaseous products. The inverse trend between the molar conversion of propylene glycol and gaseous products at different reaction
time supports this claim (Table 1 and Figure 2). One of the possible
reactions that lead to the formation of gases is the hydrocracking of
propylene glycol to ethylene glycol and methane as suggested by
Chiu and co-workers.10
On the other hand, increasing the water to glycerol mass ratio
favored more the reformation reactions than the hydrogenolysis to
propylene glycol. This explains the low yield of propylene glycol and
the high yield of gaseous products at 7:3 water to glycerol mass ratio
(Table 1 and Figure 3). Though water thwarted the yield of the
process toward propylene glycol at higher water to glycerol mass
ratios, water was still essential in inhibiting other reactions such as
dehydration of the intermediates to unwanted compounds. As
shown in Figure 3, the yield of propylene glycol decreased as the
water content in the reactant mixture was decreased from 50 to
30 wt %.
Ethanol production was also aected by the operating parameters but in a dierent way. The yield of ethanol increased as the
reaction time increased while it decreased at lower water to
glycerol mass ratios. As shown in Scheme 1, ethanol was
produced from hydrogenolysis of acetol. However, the results
of this study suggest that ethanol may have been produced from
dierent reaction routes. The observed decreasing trend of acetol
was caused by the decreasing of glycerol in the reactant rather
than being consumed in a reaction to form ethanol. More than 98
mol % glycerol had already been converted at 45 min of reaction
(Table 1). Thus, there was no more glycerol to replenish acetol
that was then further converted to propylene glycol beyond 45
min. Instead of acetol, propylene glycol reformation to ethanol
could have occurred. Following the same reaction mechanism
discussed by Wojcik and Adkins,12 hydrogenolysis of propylene
glycol can also produce ethanol, as shown in Scheme 2.
However, there was no direct correlation between the ethanol
produced and the propylene glycol degraded (Figure 2). Other
reactions such as reformation of propylene glycol to hydrogen
and carbon monoxide may have competed with the reaction
suggested in Scheme 2. Moreover, possible reformation of ethanol
to gaseous products may have occurred while it was produced
simultaneously.

The initial water content in the reactant mixture aected

ethanol yield favorably by the reformation reactions at higher
water to glycerol mass ratios. The trend observed in Figure 3
reinforces this hypothesis, in which more ethanol and gases but
less propylene glycol were produced.
In the case of methanol formation, unlike the other alcohols,
no signicant change in methanol yield in the liquid product was
observed under dierent operating conditions. This may lead to
the conclusion that methanol was a minor intermediate product
or possibly already in equilibrium with all other compounds
present in the system.
Effect of Catalyst. The application of Raney nickel catalysts
was effective in providing the activated sites for the reactions of
producing hydrogen and converting glycerol to propylene glycol
and ethanol. The direct relationship between the catalyst doses and
the glycerol conversion to propylene glycol, ethanol, and gaseous
products indicates this inference. A higher dose of catalyst increases
the pore surfaces and the active sites, thus improving the conversion
rate of glycerol. The yield of acetol was affected by the doses of
catalyst. At the low application rate of 1.0 wt % catalysts, the acetol
yield was higher than the acetol yields at 2.9 and 4.7 wt % catalyst. It
is the authors interpretation that there were not enough reactive
sites to promote hydrogenation of acetol to propylene glycol; in
turn, not all of the acetol produced through dehydration of glycerol
was consumed to the formation of propylene glycol. By increasing
the mass of the catalysts, the rate of hydrogenation reactions
increased, which caused immediate consumption of acetol and led
to the decrease of acetol in the liquid product.

CONCLUSIONS
The results of this study conrmed that propylene glycol and
ethanol can be produced from glycerol in the absence of external
hydrogen supply. Hydrogen was produced under the operating
conditions as explored in this study. Higher yield for propylene
glycol was observed at shorter reaction time and water to glycerol
mass ratio of 1:1. Water is essential in inhibiting side reactions, such
as dehydration of intermediate compounds, in propylene glycol
production. Water also promotes additional reformation reactions
that make propylene glycol degrade to other products. On the other
hand, competing with these reactions is the hydrogenolysis of
propylene glycol to ethanol. Thus, longer reaction time and
increased initial water results in higher ethanol yield.
On the basis of the results of this study, it can be proposed that
the reactions of glycerol reformation to hydrogen and hydrogenolysis to propylene glycol via the acetol pathway occur
simultaneously in the catalytic thermochemical conversion of
glycerol. These reformation reactions include carbon-to-carbon
and hydrogen
carbon bond cleavages, which produce carbon
monoxide and hydrogen, and the water-gas shift reaction, which
produces hydrogen. The hydrogen produced initiates immediately the hydrogenation of acetol to propylene glycol. On the
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basis of the results of the study, it can be concluded that ethanol is
produced through the hydrogenolysis of propylene glycol instead
of acetol in the system.

AUTHOR INFORMATION
Corresponding Author

*E-mail: [email protected].
Notes

E-mail: [email protected].

ACKNOWLEDGMENT
This study was supported nancially by the National Institute
of Advanced Transportation Technology (NIATT) and the Biological
and Agricultural Engineering Department at the University of
Idaho. The authors also express their gratitude to Dr. Joe
Thompson for his great assistance in the study. Valuable discussions with and advice from Dr. Peter Griths (professor of
Chemistry), Dr. Jon Van Gerpen (professor of Biological and
Agricultural Engineering), and Dr. Roger Korus (professor of
Chemical Engineering) are also gratefully acknowledged.
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