Glycerol1 PDF
Glycerol1 PDF
Glycerol1 PDF
pubs.acs.org/IECR
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.
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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 %)
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 %)
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 hydrogencarbon 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-
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