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 glycerol using metal catalysts. However, the production of propy-

Biodiesel is an alternative fuel produced by transesterication lene glycol from glycerol has received more attention and is mostly
of an alcohol and a plant oil or animal fat. With the introduction of researched as compared to the production of other polyhydric
the next generation feedstocks such as jatropha and algae, it is alcohols such as 1,3-propanediol and ethylene glycol.4
8 Propylene
predicted that the biodiesel production will be tripled by 2020.1 glycol is also the preferred product rather than ethylene glycol
However, along with the success of the biodiesel industry, the global because of the less desired toxic characteristics of ethylene glycol.
production of glycerol, a byproduct of biodiesel production, also Suppes and co-workers performed research on the conversion of
increased. The rapid increase in crude glycerol greatly aected the glycerol to propylene glycol and patented a process of selectively
market price of glycerol, which dropped from $0.43/kg in 2003 to producing propylene glycol.9
11 In producing propylene glycol, one
$0.18/kg in 2010 for pure glycerol, and to only $0.02/kg for crude of the primary hydroxyl groups in glycerol is selectively removed
glycerol.2,3 Although various products can be derived from glycerol through hydrogenolysis using a metal catalyst. There are two
for dierent applications, the demand for these products is still not theories in hydroxyl group selective removal, namely, the acetol
enough to handle the increasing supply of crude glycerol. Thus, new pathway and the glyceraldehyde pathway,4 of which the acetol
technologies of producing valuable products with relatively large pathway has been the most widely investigated. According to the
markets from glycerol are urgently needed. theory of acetol pathway, the secondary hydroxyl group of glycerol is
Converting glycerol to primary alcohols such as ethanol and dehydrated to acetol followed by catalytic hydrogenation to propy-
methanol, and polyhydric alcohols such as propylene glycol, through lene glycol. Therefore, hydrogen presence in the system is a must.
a thermochemical process is a potential way to increase the value of In addition to polyhydric alcohols, ethanol and methanol are
crude glycerol. Thermochemical processes can use heat only to other valuable products that can be derived from glycerol. In
break down organic matter into desired products. The problem with producing propylene glycol from glycerol, degradation of acetol
thermochemical processes is, however, the low selectivity toward and propylene glycol to other products has been reported.10
desired products. Conventional thermochemical conversions in- However, secondary reactions such as the decomposition of acetol
volve high operating temperatures. Such conditions also favor and propylene glycol can be utilized in a favorable way to produce
further decomposition and repolymerization of the desired products valuable compounds in addition to propylene glycol. Wojcik and
to undesired compounds such as char and tar. This problem can Adkins12 used hydrogenolysis to prepare specic hydrocarbons
be avoided if appropriate catalysts are employed to increase the from long-chain alcohols. In their process, the carbon with the
selectivity and eciency of the chemical process. Catalysts have the hydroxyl group is cleaved at the carbon to carbon bond from the
capability to decrease the energy required by lowering the activa- long-chain alcohol, producing a hydrocarbon, methane, and water.
tion energy of a chemical reaction and to increase the selectivity Based on this concept, further hydrogenolysis of acetol could lead to
by breaking specic chemical bonds to produce the intended ethanol formation, as shown in Scheme 1.
products. It is logical, therefore, to apply catalysts to the thermo- Theoretically, hydrothermal cracking of glycerol, i.e., the high-
chemical decomposition of glycerol to improve the selectivity temperature reaction of glycerol with water, can produce
toward the desired alcohol products.
Metal catalysts have been used in converting glycerol to Received: December 28, 2010
polyhydric alcohols and hydrogen through hydrogenolysis and Accepted: March 31, 2011
reforming, respectively. Ethylene glycol and propylene glycol are Revised: March 30, 2011
examples of useful polyhydric alcohols that can be derived from

r XXXX American Chemical Society A dx.doi.org/10.1021/ie102573m | Ind. Eng. Chem. Res. XXXX, XXX, 000000
Industrial & Engineering Chemistry Research ARTICLE

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 aqueous- Figure 1. Schematic diagram of the reactor system used in the study.
phase reforming.17
19 Steam reforming uses steam to react with an
organic compound to produce carbon dioxide and hydrogen.20
23 A 300 mL pressure reactor from Parr Instruments (Moline, IL)
Autothermal reforming is the combination of steam reforming and was used for conducting the experiments in this study. The reactor is
oxidation of glycerol.18 This is achieved by preheating a glycerol/ capable of handling up to 20 MPa (3000 psig) of pressure and
water mixture at 300 ( 10 C and feeding the vaporized mixture 350 C of temperature. The reactor is equipped with a controller to
with lean air to a reactor with a catalyst.18 The heat produced by the regulate and monitor the operating temperature, pressure, and
oxidation of glycerol is used by the steam reforming reactions to agitation motor speed. A capture vessel (a vacuum ask) was
produce hydrogen, and such a system reduces the overall energy installed along the exhaust line to capture any condensables escaping
requirement of the process. The above-mentioned processes are during removal of gases after reaction (Figure 1).
typically operated at temperatures over 400 C at atmospheric Analysis of Samples. An Agilent 6890N gas chromatograph
pressure. On the other hand, aqueous-phase reforming operates at with a flame ionization detector (FID) was used for analyzing the
higher pressures (2.5 MPa) but at relatively lower temperatures primary and polyhydric alcohols and residual glycerol. For this
(220 C).19,24 These conditions are similar to those required for purpose, the column was a 30 m by 0.32 mm inside diameter DB-
the hydrogenolysis of glycerol to propylene glycol. If hydrogen can wax column with 0.5 m film thickness. A 5 g amount of the sample
be produced from glycerol at conditions where hydrogenolysis and 100 mg of the internal standard (diethyl ether) were mixed and
occurs, it can be hypothesized that glycerol can undergo hydro- deionized water was added to make up 10 mL of solution. The
genolysis to catalytically produce valuable primary and polyhydric solution was then diluted by adding HPLC grade acetone to the
alcohols without external hydrogen supply, which is an ideal process solution to make up 50 mL of the final solution. The oven
with signicant economic advantages. temperature was programmed to begin at 30 C for 10 min before
Currently, there is no in-depth investigation reported on ramping to 220 C at 30 C/min with a final hold time of 13 min.
converting glycerol to alcohols using a catalytic thermochemical Samples of 1 L were injected with a split ratio of 60:1 and with an
process without external hydrogen supply. This study aimed to inlet port temperature of 250 C. The inlet port temperature was set
investigate the production of primary alcohols and propylene slightly lower than 290 C to prevent any glycerol decomposition.
glycol through catalytic thermochemical process with no external Slight and complete decomposition below its boiling point have
hydrogen supply and to determine the favorable conditions for been reported.25,26 Helium was used as the carrier gas with its
maximizing the same. 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
METHODS 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.
Materials and Equipment. Reagent grade glycerol (BDH Experimental Procedures. Experiments of catalytic thermo-
distributed by VWR, West Chester, PA) with 99.5% purity was chemical conversion of glycerol to alcohols were conducted using
used throughout the experiments in our first phase research to the batch reactor as described in Figure 1. Glycerol, water, and the
avoid the interference of impurities found in crude glycerol from metal catalyst were mixed in the reactor. Nitrogen gas was used to
biodiesel. Active Raney nickel catalyst was purchased from purge the headspace of the reactor for 1 min to remove oxygen. The
Sigma-Aldrich (St. Louis, MO) and used. Standards of methanol, reactor was then heated to 230 C and maintained at the set reaction
ethanol, n-propanol, 2-propanol, propylene glycol, acetol, and time. Upon the completion of the reaction, the reactor was cooled to
glycerol were prepared for calibrating the gas chromatograph. room temperature by the equipped cooling mechanism. The
Methanol (99.8% purity), acetone (99.7%), and 2-propanol noncondensable gases formed during the reaction were removed
(99.99%) were purchased from EMD (Gibbstown, NJ). Acetol through the exhaust valve and vented out. The final weight of the
(95%) and propylene glycol (99.5%) was purchased from Alfa liquid product and catalyst was determined by measuring the reactor
Aesar (Ward Hill, MA), and 1-propanol (99.9%, J.T. Baker) was with the product (liquid and catalyst) and taking the difference of
purchased from VWR (West Chester, PA). Ethanol was bought the premeasured weight of the empty reactor. The liquid product
from AAPER, Alcohol and Chem. Co. (Shelbyville, KY). Diethel collected from the reactor was separated from the catalysts using a
ether (99.0%, BDH) was purchased from VWR. vacuum filtration at constant vacuum pressure of 16.9 kPa (5 in.Hg).
B dx.doi.org/10.1021/ie102573m |Ind. Eng. Chem. Res. XXXX, XXX, 000000
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Table 1. Conversion Rates of Glycerol and Yields of Gases at 230 C Using Raney Nickel Catalysta
reaction time (min) 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
a
Each treatment was conducted in triplicate. Data are presented as average ( standard deviation. b WGMR = water to glycerol mass ratio in the feed.
c
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
glycerol conversion rate=mol %  100
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
yield of alcohol j=mol %  100
ni;gly

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

j = methanol, ethanol, or propylene glycol.
Figure 2. Alcohol yields versus reaction time. Each treatment was
ngas
conducted in triplicate, and the error bars represent the standard yield of gases=mol %  100
deviations. The symbols in the plot are as follows: 9, propylene glycol; nc;feed
2, ethanol; b, acetol.
where ngas is the moles of gases formed and nc,feed is the moles of
Whatman Qualitative No. 2 filter paper (8 m pore size) was used initial carbon in the feed.
throughout the study.
The amount of gas evolved was estimated using the modied EXPERIMENTAL RESULTS
Benedict
Webb
Rubin gas equation for real gas mixtures Effect of Reaction Time. Table 1 summarizes the experi-
(eq 1). The intermediate parameters were evaluated on the basis mental results of the overall glycerol conversion and gaseous
of the critical parameters such as temperature, density, and products at different reaction time and water to glycerol mass
acentric factor of its pure species as described by Starling and ratio. Water to glycerol mass ratio, WGMR, is defined as the ratio
Han.27 The dierence in the pressure of the reactor before and of water and glycerol used in the feed. It shows that at 45 min and
after the reaction at the same temperature, specically at 30 C, longer into the reaction, more than 98 mol % glycerol was
was assumed to represent the contribution of gas formed. Thus, converted (Table 1). In addition to liquid products, gaseous
this pressure dierence was used in the gas equation. Also, it was compounds were also formed during the reaction. The results
assumed that carbon dioxide was the dominant gas formed due to also show that more gaseous compounds were formed at
the inability to determine the composition of the gaseous extended reaction time. Pairwise analysis on the pressure read-
products in this study. ings using the least significant difference test (LSD test) at 95%
confidence level by the Statistical Analysis System software (SAS
Benedict
Webb
Rubin equation of state: Institute Inc., Cary, NC) suggested that there were significant
 
Co Do Eo differences in the amount of gases formed from 15 to 75 min
P FRT Bo RT
Ao
2 3
4 F2 while no differences were observed thereafter.
T T T
Propylene glycol and ethanol were the major liquid products
    of the process. Other simple alcohols, such as methanol and
d 3 d 6
bRT
a
F R a F 2-propanol, were also produced but in small amounts. Acetol,
T T which is the proposed intermediate compound for producing
propylene glycol and ethanol, was also present in the liquid
cF3 product. The alcohol yields against the reaction time are shown
F2 exp
F2 1
T2 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 (
where P is the absolute pressure, Pa; T is the absolute tempera- 0.7 mol %. Similarly to that of propylene glycol, the yield of acetol
ture, K; F is the gas density, mol/m3; R is the gas constant, 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 10.911 ( 0.387 8.519 ( 0.733 7.249 ( 0.326
n-propanol 0.456 ( 0.012 0.388 ( 0.028 0.380 ( 0.012
a
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.

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 conver-
sion rate increased from 49.04 to 98.59 mol % and the gas yields
Figure 3. Alcohol yields at dierent initial amounts of water in the feed. increased from 3.69 to 17.60 mol % when increased concentra-
Each treatment was conducted in triplicate, and the error bars represent tions of nickel catalyst were applied (Table 3).
the standard deviations. The symbols in the plot are as follows: 9,
propylene glycol; 2, ethanol; b, acetol.
DISCUSSION
Effect of the Initial Amount of Water. Water is an essential The presence of signicant amounts of ethanol and propylene
ingredient in producing hydrogen from glycerol through the water- glycol in the liquid product conrms that hydrogenolysis had
gas shift reaction. Thermodynamic analysis on steam reforming of occurred in the catalytic thermochemical conversion of glycerol.
glycerol showed that more hydrogen can be produced at higher The formation of gaseous products also supported the authors
water to glycerol mass ratios.20,21 For example, Luo et al.19 obtained hypothesis that a portion of glycerol has been converted to
higher hydrogen yields at 5 wt % glycerol than that at 10 wt % in hydrogen and utilized simultaneously in the production of alcohols.
water solutions at 220 C. In addition, water also helps maintain a Although the presence of hydrogen was unconrmed due to a lack
homogeneous temperature profile throughout the liquid-phase of tests for this study, we have no other explanation for the formation
reaction and inhibits chemical dehydration of glycerol to unwanted of gases other than the aqueous-phase reformation of glycerol that
intermediates and products in hydrogenolysis.10 Table 2 sum- occurs at the same conditions as in this study, which typically
marizes the yields of primary alcohols at different water to glycerol produces carbon dioxide and hydrogen.24 Methanol and n-propanol
mass ratios. The ethanol yield increased as the water content in the were also produced in the process. The low yields of methanol and
solution increases. A similar trend was observed for methanol and n-propanol, however, suggest that the conditions explored in the
gaseous products. On the other hand, less propylene glycol was study favor other competing reactions such as formation of
produced at higher water to glycerol mass ratios (Figure 3). propylene glycol.
Comparing the cases of 7:3 and 1:1 of water to glycerol mass ratios, Effect of Operating Parameters. The yield of propylene glycol
the decreasing trend of propylene glycol can be attributed to the was significantly affected by the parameters tested in this study. At
production of more gaseous compounds as manifested by the 230 C, the highest yield of propylene glycol was observed at the
increasing operating pressures (Table 1). However, this trend does shortest reaction time, i.e., 15 min. Extending the reaction time
not hold when the initial amount of water was further decreased. As resulted in degradation of propylene glycol to other products as
shown in Figure 3, propylene glycol peaked near the water to indicated by the increasing yields of ethanol and gases (Table 1 and
glycerol mass ratio of 1:1 but the amount of gaseous products still Figure 2). Maris and Davis6 also observed a decreasing trend in
kept decreasing as shown in Table 1. propylene glycol yields when the reaction time was prolonged. In
Effect of Catalyst. Figure 4 summarizes the yield trends of their study, the yield of propylene glycol peaked at the same time
alcohols at different amounts of nickel catalysts at 230 C for 45 min when almost all of the glycerol has been converted to products and
of reaction and 1:1 water to glycerol mass ratio. Increasing the doses then the yield continuously decreased thereafter. Although it took
of the catalysts resulted in the increases of the yields of both ethanol 100 min of reaction to achieve a conversion rate of glycerol greater
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Industrial & Engineering Chemistry Research ARTICLE

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 49.04 3.69 6.4 95.75 16.36

2.9 77.19 8.31 8.9 98.59 17.60
4.7 87.95 12.12

Scheme 2. Hydrogenolysis of Propylene Glycol to Ethanol 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,
than 90 mol % in the study of Maris and Davis, almost all glycerol no signicant change in methanol yield in the liquid product was
has been converted to products after 45 min in our study, as observed under dierent operating conditions. This may lead to
summarized in Table 1. Comparing it to the results from the study of the conclusion that methanol was a minor intermediate product
Maris and Davis,6 it can be concluded that the production of or possibly already in equilibrium with all other compounds
propylene glycol had reached its maximum at or earlier than 15 min. present in the system.
The degradation of propylene can also be explained by the increase Effect of Catalyst. The application of Raney nickel catalysts
of gaseous products. The inverse trend between the molar conver- was effective in providing the activated sites for the reactions of
sion of propylene glycol and gaseous products at different reaction producing hydrogen and converting glycerol to propylene glycol
time supports this claim (Table 1 and Figure 2). One of the possible and ethanol. The direct relationship between the catalyst doses and
reactions that lead to the formation of gases is the hydrocracking of the glycerol conversion to propylene glycol, ethanol, and gaseous
propylene glycol to ethylene glycol and methane as suggested by products indicates this inference. A higher dose of catalyst increases
Chiu and co-workers.10 the pore surfaces and the active sites, thus improving the conversion
On the other hand, increasing the water to glycerol mass ratio rate of glycerol. The yield of acetol was affected by the doses of
favored more the reformation reactions than the hydrogenolysis to catalyst. At the low application rate of 1.0 wt % catalysts, the acetol
propylene glycol. This explains the low yield of propylene glycol and yield was higher than the acetol yields at 2.9 and 4.7 wt % catalyst. It
the high yield of gaseous products at 7:3 water to glycerol mass ratio is the authors interpretation that there were not enough reactive
(Table 1 and Figure 3). Though water thwarted the yield of the sites to promote hydrogenation of acetol to propylene glycol; in
process toward propylene glycol at higher water to glycerol mass turn, not all of the acetol produced through dehydration of glycerol
ratios, water was still essential in inhibiting other reactions such as was consumed to the formation of propylene glycol. By increasing
dehydration of the intermediates to unwanted compounds. As the mass of the catalysts, the rate of hydrogenation reactions
shown in Figure 3, the yield of propylene glycol decreased as the increased, which caused immediate consumption of acetol and led
water content in the reactant mixture was decreased from 50 to to the decrease of acetol in the liquid product.
30 wt %.
Ethanol production was also aected by the operating param-
eters but in a dierent way. The yield of ethanol increased as the CONCLUSIONS
reaction time increased while it decreased at lower water to The results of this study conrmed that propylene glycol and
glycerol mass ratios. As shown in Scheme 1, ethanol was ethanol can be produced from glycerol in the absence of external
produced from hydrogenolysis of acetol. However, the results hydrogen supply. Hydrogen was produced under the operating
of this study suggest that ethanol may have been produced from conditions as explored in this study. Higher yield for propylene
dierent reaction routes. The observed decreasing trend of acetol glycol was observed at shorter reaction time and water to glycerol
was caused by the decreasing of glycerol in the reactant rather mass ratio of 1:1. Water is essential in inhibiting side reactions, such
than being consumed in a reaction to form ethanol. More than 98 as dehydration of intermediate compounds, in propylene glycol
mol % glycerol had already been converted at 45 min of reaction production. Water also promotes additional reformation reactions
(Table 1). Thus, there was no more glycerol to replenish acetol that make propylene glycol degrade to other products. On the other
that was then further converted to propylene glycol beyond 45 hand, competing with these reactions is the hydrogenolysis of
min. Instead of acetol, propylene glycol reformation to ethanol propylene glycol to ethanol. Thus, longer reaction time and
could have occurred. Following the same reaction mechanism increased initial water results in higher ethanol yield.
discussed by Wojcik and Adkins,12 hydrogenolysis of propylene On the basis of the results of this study, it can be proposed that
glycol can also produce ethanol, as shown in Scheme 2. the reactions of glycerol reformation to hydrogen and hydro-
However, there was no direct correlation between the ethanol genolysis to propylene glycol via the acetol pathway occur
produced and the propylene glycol degraded (Figure 2). Other simultaneously in the catalytic thermochemical conversion of
reactions such as reformation of propylene glycol to hydrogen glycerol. These reformation reactions include carbon-to-carbon
and carbon monoxide may have competed with the reaction and hydrogen
carbon bond cleavages, which produce carbon
suggested in Scheme 2. Moreover, possible reformation of ethanol monoxide and hydrogen, and the water-gas shift reaction, which
to gaseous products may have occurred while it was produced produces hydrogen. The hydrogen produced initiates immedi-
simultaneously. ately the hydrogenation of acetol to propylene glycol. On the
E dx.doi.org/10.1021/ie102573m |Ind. Eng. Chem. Res. XXXX, XXX, 000000
Industrial & Engineering Chemistry Research ARTICLE

basis of the results of the study, it can be concluded that ethanol is (15) Valliyappan, T.; Ferdous, D.; Bakhshi, N. Production of Hydro-
produced through the hydrogenolysis of propylene glycol instead gen and Syngas via Steam Gasication in a Fixed-Bed Reactor. Top.
of acetol in the system. Catal. 2008, 49, 59.
(16) Zhang, B.; Tang, X.; Li, Y.; Xu, Y.; Shen, W. Hydrogen
AUTHOR INFORMATION Production from Steam Reforming of Ethanol and Glycerol over
Ceria-Supported Metal Catalysts. Int. J. Hydrogen Energy 2007, 32, 2367.
Corresponding Author (17) Buoni, I.; Pompeo, F.; Santori, G.; Nichio, N. Nickel Catalysts
*E-mail: [email protected]. Applied in Steam Reforming of Glycerol for Hydrogen Production.
Catal. Commun. 2009, 10, 1656.
(18) Dauenhauer, P.; Salge, J.; Schmidt, L. Renewable Hydrogen by
Notes
Autothermal Steam Reforming of Volatile Carbohydrates. J. Catal. 2006,
E-mail: [email protected]. 244, 238.
(19) Luo, N.; Fu, X.; Cao, F.; Xiao, T.; Edwards, P. Glycerol Aqueous
Phase Reforming for Hydrogen Generation over Pt CatalystsEect of
ACKNOWLEDGMENT Catalyst Composition and Reaction Conditions. Fuel 2008, 87, 3483.
This study was supported nancially by the National Institute (20) Adhikari, S.; Fernando, S.; Gwaltney, S. R.; Filip To, S. D.;
of Advanced Transportation Technology (NIATT) and the Biological Bricka, R. M.; Steele, P.; Haryanto, A. A Thermodynamic Analysis of
Hydrogen Production by Steam Reforming of Glycerol. Int. J. Hydrogen
and Agricultural Engineering Department at the University of
Energy 2007, 32, 2875.
Idaho. The authors also express their gratitude to Dr. Joe (21) Adhikari, S.; Fernando, S.; Haryanto, A. A Comparative Ther-
Thompson for his great assistance in the study. Valuable discus- modynamic and Experimental Analysis on Hydrogen Production by
sions with and advice from Dr. Peter Griths (professor of Steam Reforming of Glycerin. Energy Fuels 2007, 21, 2306.
Chemistry), Dr. Jon Van Gerpen (professor of Biological and (22) Adhikari, S.; Fernando, S.; Haryanto, A. Production of Hydro-
Agricultural Engineering), and Dr. Roger Korus (professor of gen by Steam Reforming of Glycerin over Alumina-Supported Metal
Chemical Engineering) are also gratefully acknowledged. Catalysts. Catal. Today 2007, 129, 355.
(23) Adhikari, S.; Fernando, S.; To, S.; Bricka, R.; Steele, P.;
Haryanto, A. Conversion of Glycerol to Hydrogen via a Steam Reform-
REFERENCES ing Process over Nickel Catalysts. Energy Fuels 2008, 22, 1220.
(1) Biofuels Market to Triple by 2020, Jun. 15, 2009. Biodiesel (24) Wen, G.; Xu, Y.; Ma, H.; Xu, Z.; Tian, Z. Production of
Magazine, http://www.biodieselmagazine.com (accessed Aug. 7, 2010). Hydrogen by Aqueous-Phase Reforming of Glycerol. Int. J. Hydrogen
(2) Lefebvre, B. Glycerine (US Gulf) ICIS Pricing, June 2010, ICIS Energy 2008, 33, 6657.
Pricing, www.icispricing.com (accessed Dec. 20, 2010). (25) Hodgman, C.; Weast, R. S.; Selby, S. CRC Handbook of
(3) Hartenbower, B.; French, W.; Hernandez, R.; Licha, M.; Benson, Chemistry and Physics: A Ready-Reference Book of Chemical and Physical
T. Biogas Production Using Glycerol, the Biodiesel By-Product, as the Data, 44th ed.; Chemical Rubber: Cleveland, OH, 1962.
Carbon Source, http://aiche.confex.com/aiche/2006/techprogram (26) Miall, L. A New Dictionary of Chemistry, 3rd ed.; InterScience:
(accessed Apr. 25, 2010), The 2006 Annual Meeting: Fuels and New York, 1961.
Petrochemical Division. (27) Starling, K.; Han, M. Thermo Data Rened for LPG14.
(4) Allhanash, A.; Koszhevnikova, E.; Kozhevnikov, I. Hydrogeno- Mixtures. Hydrocarbon Process. (1966
2001) 1972, 51, 129132.
lysis of Glycerol to Propanediol over Ru:Polyoxymetalate Bifunctional
Catalyst. Catal. Lett. 2008, 120, 307.
(5) Huang, Z.; Cui, F.; Kang, H.; Chen, J.; Zhang, X.; Xia, C. Highly
Dispersed Silica-Supported Copper Nanoparticles Prepared by Precipi-
tation-Gel Method: A Simple but Ecient and Stable Catalyst for
Glycerol Hydrogenolysis. Chem. Mater. 2008, 20, 5090.
(6) Maris, E.; Davis, R. Hydrogenolysis of Glycerol over Carbon-
supported Ru and Pt Catalysts. J. Catal. 2007, 249, 328.
(7) Meher, L.; Gopinath, R.; Naik, S.; Dalai, A. Catalytic Hydro-
genolysis of Glycerol to Propylene Glycol over Mixed Oxides Derived
from a Hydrotalcite-type Precursor. Ind. Eng. Chem. Res. 2009, 48, 1840.
(8) Miyazawa, T.; Koso, S.; Kunimoro, K.; Tomishige, K. Glycerol
Hydrogenolysis to 1,2-Propanediol Catalyzed by a Heat-Resistant Ion-
Exchange Resin Combined with Ru/C. Appl. Catal., A 2007, 329, 30.
(9) Chiu, C.; Dasari, M.; Suppes, G.; Sutterlin, W. Dehydration of
Glycerol to Acetol via Catalytic Reactive Distillation. AIChE J. 2006, 52, 3543.
(10) Chiu, C.; Tekeei, A.; Ronco, J.; Banks, M.; Suppes, G. Reducing
Byproduct Formation during Conversion of Glycerol to Propylene
Glycol. Ind. Eng. Chem. Res. 2008, 47, 6878.
(11) Suppes, G.; Sutterlin, W. Method of Producing Lower Alcohols
from Glycerol. World Intellectual Property Organization, WO 2007/
053705 A2, 2007.
(12) Wojcik, B.; Adkins, H. Hydrogenolysis of Alcohols to Hydro-
carbons. J. Am. Chem. Soc. 1933, 55, 1293.
(13) Hirai, T.; Ikenaga, N.; Miyake, T.; Suzuki, T. Production of
Hydrogen by Steam Reforming of Glycerin on Ruthenium Catalyst.
Energy Fuels 2005, 19, 1761.
(14) Slinn, M.; Kendall, K.; Mallon, C.; Andrews, J. Steam Reform-
ing of Bio-diesel By-product to Make Renewable Hydrogen. Bioresour.
Technol. 2008, 99, 5851.

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