Energy & Fuels 2007, 21, 34993504

3499

Experimental Investigation of Hydrogen Production from Glycerin

Reforming
Aurelien M. D. Douette, Scott Q. Turn,* Wuyin Wang, and Vheissu I. Keffer
Hawaii Natural Energy Institute, UniVersity of Hawaii, 1680 East West Road,
POST 109, Honolulu, Hawaii 96822
ReceiVed August 14, 2006. ReVised Manuscript ReceiVed July 6, 2007

A series of tests were performed to investigate reforming of reagent-grade propane-1,2,3-triol, (C3H8O3)

commonly called glycerin, to produce a H2 rich gas. Effects of the operating parameters, oxygen to carbon
ratio, steam to carbon ratio, and temperature, were determined using a factorial experimental design. A
mathematical model defining the effect of the three parameters was derived and used to improve the hydrogen
yield. From the range of experimental conditions, it was concluded that the oxygen to carbon ratio, as well as
the interaction between oxygen to carbon ratio and temperature had the most important effects on H2 yield. A
4.5 mol quantity of hydrogen was produced per mole of glycerin at experimental conditions of oxygen to
carbon ratio of 0, steam to carbon ratio of 2.2, and temperature of 804 C. This is 65% of the maximum
theoretical H2 yield, and 90% of the H2 yield predicted by thermochemical equilibrium. A 1.4 mol quantity of
CO was also produced per mole of glycerin, presenting the potential for additional production of 1.4 mol
H2/mol glycerin. A water gas shift reactor was added to the process and operated at 369 C, producing a final
yield of 5.3 mol H2/mol glycerin, 75% of the maximum stoichiometric hydrogen yield. Crude glycerin obtained
from biodiesel production was finally tested (without the water gas shift reactor) as a feed and compared with
reagent-grade glycerin results. The initial crude glycerin hydrogen yield, 4.4 mol H2/mol glycerin, was almost
identical to that of reagent-grade glycerin, but carbon formation and coking increased the pressure drop through
the catalyst bed causing the test to be terminated. Possible contaminants, chloride and sodium cations, present
in crude glycerin as byproducts of biodiesel synthesis were added to reagent-grade glycerin and tested in the
reformer, producing results similar to those observed for the crude glycerin reforming test.

Introduction
Society is increasingly looking for clean and renewable fuels
to offset the negative effects of fossil fuel use including
greenhouse gas emissions and consumption of limited resources.
Two possible renewable energy supplies are biodiesel and
hydrogen. The U.S. has a biodiesel production capacity of about
350 million gallons with a 2005 production of 100 million
gallons.1 Ten million gallons of crude glycerin (C3H8O3, IUPAC
name propane-1,2,3-triol) were also produced as byproduct.
Biodiesel has become more competitive against petroleum diesel
due to the higher prices of crude oil and increased demand for
environmentally acceptable fuels. It is anticipated that biodiesel
and crude glycerin production will continue to grow. Hydrogen
is a clean energy source with uses including ammonia production, petroleum processing, and power generation in fuel cells.26
Fossil fuels are currently used as the feed stock to satisfy 95%
of U.S. hydrogen demand, and steam reforming of natural gas
* Corresponding author. E-mail: sturn@hawaii.edu.
(1) Butzen, S. Biodiesel production in the U.S. Pioneer, A Dupont
Company. http://www.pioneer.com/CMRoot/Pioneer/media_room/biofuels/
documents/biodiesel.pdf (accessed Aug 2006).
(2) Ramachandran, R.; Menon, R. K. Int. J. Hydrogen Energy 1998,
23, 593598.
(3) Ancheyta, J.; Rana, M. S.; Furimsky, E. Catal. Today 2005, 109,
12.
(4) Prins, R.; Egorova, M.; Rthlisberger, A.; Zhao, Y.; Sivasankar, N.;
Kukula, P. Catal. Today 2006, 111, 8493.
(5) Long, F. X.; Gevert, B. S. J. Catal. 2004, 222, 15.
(6) Alcaide, F.; Cabot, P. L.; Brillas, E. J. Power Sources 2006, 153,
4760.

accounts for 48%.7 Reforming is a potential method for

obtaining renewable hydrogen from crude glycerin.
Reforming reactions are generally endothermic, and a reforming process may be characterized as steam reforming, catalytic
partial oxidation, or autothermal reforming depending upon the
source of heat and types of reactants.8 A general equation to
describe glycerin reforming is shown in eq 1.
C3H8O3 + xH2O + yO2 f aCO2 + bCO
+ cH2O + dH2 + eCH4 + ... (1)
External heat may be provided to the process as in the case
of steam reforming (eq 1: x > 0, y ) 0) or an oxygen source
may be included to react with the feed stock and provide the
required heat internally as in the case of catalytic partial
oxidation (eq 1: x ) 0, y > 0) and autothermal reforming (eq
1: x > 0, y > 0). The amounts of H2O and O2 added as reactants
are reported relative to the carbon input in the feed stock, i.e.,
molar ratios of steam to carbon (S) and O2 to carbon (O). In
this case, O includes only O2 added in pure form or air and
does not include oxygen present in steam or in the fuel. The
equilibrium composition depends on these reactant ratios and
the reaction temperature (T) and pressure. As indicated in eq 1,
reforming products include hydrogen and carbon monoxide as
(7) National Hydrogen Vision Meeting. A National Vision of Americas
Transition to a Hydrogen Economy- To 2030 and Beyond. United States
Department of Energy. www1.eere.energy.gov/hydrogenandfuelcells/pdfs/
vision_doc.pdf (accessed Feb 2002).
(8) Joensen, F.; Rostrup-Nielsen, J. R. J. Power Sources, 2002, 105,
195201.

10.1021/ef060379w CCC: $37.00 2007 American Chemical Society

Published on Web 09/05/2007

3500 Energy & Fuels, Vol. 21, No. 6, 2007

well as carbon dioxide and methane.9 A catalyst is used to

accelerate the reactions in the reforming process. Ni, Co, Ni/
Cu, and noble metal (Pd, Pt, Rh) based catalysts all favor
hydrogen production with Ni being the most commonly used.
Catalysts enhance the reforming reaction rates at the molecular
level and thorough discussions of the topic are available in the
literature.1014
This paper presents results of experiments using glycerin as
a reforming feed stock for hydrogen production. Crude glycerin
obtained from biodiesel production may contain impurities such
as NaCl, NaOH, methanol, and free fatty acids as a result of
the biodiesel manufacturing process. Crude glycerin composition
varies from batch to batch, and therefore, reagent-grade glycerin
was initially used to remove the effect of contaminants from
the experiments. Afterward, crude glycerin and reagent-grade
glycerin doped with contaminants were tested and compared
with reagent-grade glycerin results.
Stoichiometric steam reforming provides an upper yield limit
of 7 mol H/mol glycerin as shown in eq 2. This theoretical yield
served as a benchmark for comparison with experimental results.

Douette et al.

Figure 1. Schematic of glycerin, nitrogen, and oxygen injection system.

Diameters of the inner, middle, and outer tubes are 0.03, 6, and 12
mm, respectively.

C3H8O3 + 3H2O f 3CO2 + 7H2 H298K ) 345 kJ/mol (2)

Experimental Section
A 20 L sample of crude glycerin byproduct was obtained
from biodiesel produced from fat, oil, and grease recovered from
food service activities (Pacific Biodiesel, Honolulu, HI). A
subsample was subjected to proximate (volatile matter, ash, and
fixed carbon), ultimate (C, H, O, N, S, ash), and heating value
analyses. A sample of the ash was analyzed for the elements
Si, Al, Ti, Fe, Ca, Mg, Na, K, and P. The bulk sample was also
analyzed for selected metals including As, B, Cd, Pb, Mn, Hg,
Mo, Se, and Zn. All analyses were performed by Hazen
Research Inc. (Golden, CO). Reagent-grade glycerin obtained
from Fisher Scientific (glycerin certified ACS, G33-1) was also
used in the reforming tests.
A laboratory scale reactor was used to study the effects of
operating conditions on the yield of hydrogen obtained from
reforming reagent-grade glycerin based on a 23 experimental
design. The reforming reaction took place in a stainless steel
pipe, 294 mm in length with an internal diameter of 25 mm.
The reactor was placed inside a furnace to provide temperature
control. Six pellets (19.6 g) of nickel-based catalyst (G-91 EW
steam reforming catalyst, Sd-Chemie Inc., Louisville, KY) were
placed in the reformer, 16 cm from the entrance. Previous
experiments with liquified petroluem gas (LPG) indicated that
this amount of catalyst was adequate for the carbon feed rate
of 0.25 mol/min.10 Flows of a liquid phase glycerin and water
mixture and gas phase oxygen and nitrogen were metered to
the reformer. Air could have been used for this experiment, but
operating experience showed it to be more practical to separate
the nitrogen and oxygen flows. Glycerin, O2, and N2 were
introduced to the reactor through three concentric tubes as shown
in the Figure 1. Typically, a 38% glycerin and 62% water
mixture was injected into the reformer through the 0.03 mm
internal diameter center tube at a rate of 3 mL/min. The mixture
(9) Song, X.; Guo, Z. Energy ConVers. Manage. 2006, 47, 560569.
(10) Wang, W.; Turn, S. Q.; Keffer, V.; Douette, A. Parametric Study
of Authothermal Reforming of LPG. Prepr. Pap.Am. Chem Soc., DiV. Fuel
Chem. 2004, 481, 142.
(11) Song, X.; Guo, Z. Energy ConVers. Manage. 2006, 47, 560569.
(12) Nurunnabi, M.; Mukainakano, Y.; Kado, S.; Li, B.; Kunimori, K.;
Suzuki, K.; Fujimoto, K.; Tomishige, K. Appl. Catal., A: General 2006,
299, 145156.
(13) Hou, K.; Hughes, R. Chem. Eng. J. 2001, 82, 311328.
(14) Sehested, J. Catal. Today 2006, 111, 103110.

Figure 2. Thermocouples and catalyst positions inside the reformer

(distances in centimeters).

percentages were determined by first choosing the water to

carbon molar ratio for the experimental conditions and then
converting this ratio to a volumetric mixture for water and
glycerin. Nitrogen (1.75 L/min) was introduced in the annulus
between the glycerin injector and a 6 mm tube, and the oxygen
was introduced into the annulus between the 6 mm tube and an
outer 12 mm tube. The nitrogen acted as a shroud gas to prevent
the oxygen from immediately reacting with the glycerin at the
injector tip. Gas flows were metered using mass flow controllers
(Model 5890e, Brooks Instruments, Hatfield, PA), and liquid
flow was regulated using a precision pump (Model QG50, FMI
Pump, Soyesset, NY).
An in-line sintered stainless steel filter was located 125 mm
downstream of the pipe to collect any particulate matter
produced in the reformer and protect downstream analytical
equipment. System pressure was monitored at the reactor inlet.
As shown in Figure 2, three, type K thermocouples were located
inside the reformer, two upstream of the catalyst and one
downstream of the catalyst, to monitor reactor temperatures.
The reactor operating conditions (pressure and temperature) were
monitored and recorded every 3 s and any sudden changes in
operating conditions were readily observed.
The gas exiting the reformer passed through a condenser to
remove water vapor and was then disposed. The reformate
stream was sampled and analyzed using a GC (Shimadzu 14A)
equipped with a thermal conductivity detector and packed
column (Carboxen 1000, Supelco, Bellafonte, PA). The GC was
equipped with an automatic sampling valve that injected a
sample every 35 min. The sample loop was purged for 3 min
prior to each injection to ensure that fresh reformate was
sampled.
A 23 factorial experimental design15 was used to study the
effects of the oxygen to carbon ratio (O), steam to carbon ratio
(15) Box, G. E. P.; Hunter, W.; Hunter, J. S. Statistics for Experimenters:
An Introduction to Design, Data Analysis, and Model Building; John Wiley
& Sons: New York, 1978.

Hydrogen Production from Glycerin Reforming

Energy & Fuels, Vol. 21, No. 6, 2007 3501

Table 1. Initial Reformer Conditions in Real and Coded Units

variable values

Table 2. Reformate Gas Component Yields

mol/mol glycerin (average ( standard deviation)

coded values

condition no.

T (C)

X1

X2

X3

condition no.

H2

CO

CO2

CH4

1
2
3
4
5
6
7
8
9
10

0.4
0.7
0.4
0.7
0.4
0.7
0.4
0.7
0.55
0.55

2.0
2.0
2.7
2.7
2.0
2.0
2.7
2.7
2.4
2.4

770
770
770
770
850
850
850
850
810
810

-1
1
-1
1
-1
1
-1
1
0
0

-1
-1
1
1
-1
-1
1
1
0
0

-1
-1
-1
-1
1
1
1
1
0
0

1
2
3
4
5
6
7
8
9
10

3.2 ( 0.1
1.5 ( 0.5
3.1 ( 0.1
1.9 ( 0.2
3.5 ( 0.1
1.3 ( 0.1
3.5 ( 0.3
1.2 ( 0.1
2.1 ( 0.1
2.1 ( 0.05

1.0 ( 0.03
0.5 ( 0.2
0.8 ( 0.03
0.5 ( 0.3
1.2 ( 0.03
0.7 ( 0.07
1.0 ( 0.1
0.6 ( 0.05
0.8 ( 0.1
0.8 ( 0.04

2.0 ( 0.01
2.3 ( 0.3
2.0 ( 0.02
2.4 ( 0.2
1.9 ( 0.02
2.2 ( 0.02
2.0 ( 0.1
2.3 ( 0.05
1.9 ( 0.02
2.2 ( 0.04

0.03 ( 0.001
0.02 ( 0.006
0.027 ( 0.001
0.008 ( 0.001
0.04 ( 0.001
0.03 ( 0.002
0.04 ( 0.003
0.03 ( 0.003
0.04 ( 0.006
0.04 ( 0.008

(S), reformer temperature (T), and the interaction of the three

variables on hydrogen yield and hydrogen concentration produced from reforming glycerin. Initial reforming conditions were
chosen based on literature review and thermochemical equilibrium calculations. The initial condition for the three variables
under study were O ) 0.55 (mol O2/mol C), S ) 2.35 (mol
H2O/mol C) and T ) 810 C. O was varied by (0.15 to 0.4
and 0.7, S was varied by (0.35 to 2.0 and 2.7, and the
temperature was varied by (40 C to 770 and 850 C. Table 1
summarizes the values of the original test conditions including
two center points (conditions 9 and 10). Coding was used to
make the statistical analysis easier. In coded units, X1, X2, and
X3 represent O, S, and T, respectively. A zero value represents
the center point for the variable, and +1 and -1 represent the
upper and lower values for the three variables under study. The
performance of the experiment is defined primarily by studying
the H2 yield (mol H2/mol glycerin) and also yields of CO, CO2,
and CH4. On the basis of results from these initial experiments,
response surface methodology was used to improve the process
performance by varying S, O, and T. For each condition (110),
the reformate gas was analyzed for the predominant gases, N2,
H2, CO, CO2 and CH4, and the trace gases, C2H6 and C2H4.
Gas yield was computed based on the measured nitrogen
concentration in the reformate (GC analysis) and the known
flow rate of nitrogen through the reactor.
After optimizing the reforming process, a water gas shift
reactor was added in series with the reformer to investigate its
effect on hydrogen production. The experiments used a monolithic water gas shift (WGS) catalyst on a nanoparticle, ceriabased, mixed oxide support (NexTech Materials, Ltd., Lewis
Center, OH). Temperature was the only variable changed in
tests of the shift reactor performance, and the reformer was
operated at the optimum conditions identified earlier.
Tests were characterized by an initial transient period until
steady experimental conditions were attained as indicated by
stable pressure and temperature profiles within the reactor. After
reaching steady state, the test was continued until six gas
samples were obtained (3.5 h) or until it failed due to the
reactor becoming plugged as indicated by increasing pressure.
Each test condition indicated in Table 1 was conducted
separately. After each test, the reactor was opened and cleaned
and prepared with fresh catalyst for the ensuing test.
Results and Discussion
Reformer. Results of the initial 23 factorial design are
presented in Table 2. H2 yield ranged from 1.2 to 3.5 mol H2/
mol glycerin. CO and CO2 yields ranged from 0.5 to 1.0 mol/
mol glycerin and 1.9 to 2.3 mol/mol glycerin, respectively. CH4
yields were less than 0.04 mol/mol glycerin for all test
conditions. From the results, mathematical models describing
the H2, CO, and CH4 yields (YH2, YCO, and YCH4, respectively)

as functions of the coded units for S, O, and T were derived;

see eqs 3, 4, and 5. Experimental values of species yield plotted
against the values predicted by the models are shown in Figure
3 and are in close agreement in all three cases.
YH2 ) 2.3 - 0.93X1 + 0.034X2 - 0.02X3 + 0.06X1X2
- 0.18X1X3 - 0.047X2X3 - 0.08X1X2X3 (3)
YCO ) 0.79 - 0.21X1 + 0.06X2 - 0.09X3 + 0.04X1X2
- 0.12X1X3 - 0.012X2X3 - 0.01X1X2X3 (4)
YCH4 ) 0.27 - 0.0054X1 + 0.0011X2 - 0.006X3 + 0.0X1X2
- 0.0011X1X3 - 0.0019X2X3 - 0.001X1X2X3 (5)
Equations 3 and 4 show that X1 (i.e., O in coded units), had
the greatest effect on H2 and CO yields. H2 yield was also
affected to a lesser extent by the interaction between O and T.
The steam to carbon ratio had very little effect on the hydrogen
yield. Methane yields were affected equally by O and T as
shown in eq 5. Following surface response methodology, eq 3
was used to determine new values of O, S, and T (see Table 3)
predicted to improve YH2 along a path of steepest ascent.
Equation 3 shows that to improve YH2, O had to be decreased
while almost keeping S and T at their center point values from
the original test conditions. Table 4 shows the gas yields for
reforming experiments conducted at conditions 11 and 12. By
minimizing the oxygen input (a reduction of 52% from the
center point), the hydrogen yield was improved from 2 to 4.5
mol H2/mol glycerin, i.e., 65% of the theoretical yield (7 mol
H2/mol glycerin) in eq 2. A 1.4 mol portion of CO was also
produced, which could theoretically produce another 1.4 mol
of H2 by the water gas shift reaction as shown in eq 6.
CO + H2O f CO2 + H2

H298K ) 41 kJ/mol

(6)

The amount of carbon monoxide increased in comparison to

conditions 110, showing that the reduced O2 input produced
more CO instead of CO2. Figure 4 shows the reformate hydrogen
and carbon monoxide concentrations for the 12 test conditions.
The experimental results were compared against the equilibrium
composition predicted using FactSage, a thermochemical software and database package. At the values of O, S, and T used
for condition 12, thermochemical equilibrium predicted 5.4 mol
H2/mol glycerin. The experimental value of 4.5 mol H2/mol
glycerin thus achieved 83% of equilibrium.
Water Gas Shift. The water gas shift optimal temperature
was reached following the same surface response approach used
to improve the reformer operation. Figure 5 shows the H2 yields
obtained operating the reformer and the water gas shift in series.
The hydrogen yield per mole of glycerin increased from 4.5
mol H2/mol glycerin exiting the reformer to 5.3 mol H2/mol
glycerin when the WGS was used, an improvement of 18%.
Also, the amount of CO2 rose from 1.4 to 2.2 mol H2/mol
glycerin, and the CO decreased from 1.4 to 0.5 mol H2/mol

3502 Energy & Fuels, Vol. 21, No. 6, 2007

Douette et al.

Figure 3. H2, CO, and CO2 yield: actual vs predicted value.

Table 3. Experimental Conditions Determined from Response
Surface Analysis
Variables
condition no.

T (C)

11
12

0.3
0

2.3
2.2

807
804

Table 4. H2, CO, and CO2 Yields from Conditions along Path of
Steepest Ascent
mole/mole glycerin
condition no.

H2

CO

CO2

11
12

3.8 ( 0.07
4.5 ( 0.08

1.0 ( 0.03
1.4 ( 0.04

1.9 ( 0.02
1.4 ( 0.02

glycerin. These results are in keeping with the water gas shift
reaction (eq 6), since the CO2 and H2 production each increased
by 0.8 mol and the CO production decreased by 0.9, showing
that approximately all the CO is converted to CO2.
If the water gas shift was the only reaction taking place in
the shift reactor, an additional 0.1 mol of CO2 should have been
produced to complete the carbon balance. The gas analysis
showed that 0.065 mol of C2H6 was produced per mole glycerin,
compared to 0.01 mol/mol glycerin at the reformer exit for
condition 12. This could account for the 0.1 difference between
the CO and CO2 yields. The carbon balance computed for the
final condition was 97.6% indicating that the measurement of
system inputs and outputs are in close agreement. The addition
of the shift reactor to the reformer improved hydrogen yield
from 64% to 75% of the maximum theoretical yield.
Catalyst Deactivation. Catalyst deactivation occurred over
time mainly due to coking and resulted in a lower hydrogen

yield.10,1620 An indicator of catalyst deactivation is an increase

in methane production, and to a lesser extent, ethane. A decrease
in reformer performance was noticeable after a few hours of
testing. For condition 12 (i.e., best reforming condition), the
hydrogen yield decreased from 4.8 to 4.5 mol H2/mol glycerin
during the first three hours, a reduction of at 2.1% per h. Figure
6 shows the hydrogen yield calculated from successive GC
samples at 35 min intervals. During the same time period, the
methane production increased from 0.1 to 0.16 mol CH4/mol
glycerin, or 20% per h. The effects of S and O on methane
production (and catalyst deactivation) were studied using the
data from the original design (i.e., conditions 18). Similar levels
of methane production were found for both low and high S
values. Comparing the methane production for the low and high
O values showed a 30% lower methane production for the higher
oxygen input. For O ) 0.4, YCH4 ) 0.033 mol CH4/mol glycerin,
and for O ) 0.7, YCH4 ) 0.023. At condition 12, where O ) 0
(no external O2 was supplied), methane production was 0.1 mol/
mol glycerin.
The lower methane production at higher oxygen to carbon
ratios is explained by the fact that supplemental oxygen helps
prevent carbon deposition on the catalyst surface thereby
maintaining catalyst activity.10,17 Carbon deposits were readily
(16) Cheekatamarla, P. K.; Lane, A. M. J. Power Sources, 2005, 152,
256263.
(17) Hardiman, K. M.; Cooper, C. G.; Adesina, A. A.; Lange, R. Postmortem characterization of coke-induced deactivated alumina-supported
CoNi catalysts. Chem. Eng. Sci. 2006, 61, 25652573.
(18) Rakass, S.; Oudghiri-Hassani, H.; Rowntree, P.; Abatzoglou, N.
Steam reforming of methane over unsupported nickel catalysts. J. Power
Sources 2006, 158, 485496.
(19) Akande, A J.; Idem, R. O.; Dalai, A. K. Appl. Catal., A: General
2005, 287, 159175.
(20) Melo, F.; Naphtha, N. M. Catal. Today 2005, 107108, 458466.

Hydrogen Production from Glycerin Reforming

Energy & Fuels, Vol. 21, No. 6, 2007 3503

Figure 4. H2 and CO concentrations (vol %, dry basis) in reformate gas for conditions 112 (see Tables 1 and 4 for experimental conditions
associated with the numbers in the legend).

Figure 5. Hydrogen yield as a function of water gas shift temperature

with the reformer operated at condition 12.

apparent on the catalyst pieces closest to the reformer inlet when

they were recovered after a test was completed. Catalyst pieces
farthest downstream kept their original, grayish color. The
amount of carbon recovered from the reformer and the filter
after each test was small (0.361.0 g), accounting for less than
1% of the total carbon contained in the glycerin feed. A
secondary impact of carbon formation was an increase in
reformer operating pressure over the test duration. A higher S/C
could be expected to reduce coking and slow the catalyst
deactivation. From the amount of carbon collected in the
reformer and the pressure recorded in the reformer, it was not
possible to determine a clear effect of S/C on the carbon
formation for the duration of these tests. The label of the reagentgrade glycerin used in the reforming tests indicated that sulfur
(as sulfate) impurities could also be present at levels of
<0.0002%. The presence of sulfur at this level could have
contributed to reduced catalyst performance.
Crude Glycerin Tests. Crude glycerin reforming tests were
conducted at the same conditions used for reagent-grade
glycerin, i.e., O ) 0.0, S ) 2.21, T ) 804 C. The process
worked well for the first hour with YH2 ) 4.4 mol H2/mol
glycerin, compared to 4.5 with reagent-grade glycerin. (Although
the crude glycerin contained impurities, the hydrogen yield

values were computed assuming a feed rate of pure glycerin.)

Methane yield (0.23 mol CH4/mol glycerin) was more than twice
the amount observed when reforming reagent-grade glycerin,
and the yields of CO and CO2 were markedly lower, each at
1 mol/mol glycerin. In addition, C2H4 was produced at levels
equal to methane, where previously it was negligible in all runs
performed using reagent-grade glycerin. The hydrogen yield
decreased quickly after the second sample (-0.41 mol H2/mol
glycerin h), and the amount of CH4 and C2H4 increased (+0.072
mol/h), indicating catalyst deactivation and poor system performance. The pressure quickly increased past 69 kPa (the limit
for the pressure sensor), and the experiment was terminated.
After the reformer was cooled down and opened, it was found
to be filled with sintered deposits. It was not possible to tell
how much carbon was in the reformer because it could not be
removed. The carbon balance on this test showed that only 2.5
mol of C were recovered in the gas phase per mole of glycerin
(83% recovery). This test showed that crude glycerin can be
reformed with high hydrogen yield but that contaminants can
cause severe coking during the reforming process. The analysis
of crude glycerin samples from Pacific Biodiesel shown in Table
5 indicates that ash, nitrogen, and sulfur accounted for 1.2, 0.19,
and 0.01% (mass), respectively. Analysis of the ash recovered
from the sample showed that potassium was the major component, equal to 0.5% of crude glycerin mass. As, Mn, and Zn
were the only metals present at levels above instrument detection
limits, and all were present at sub-ppm levels. The major
contaminants known to be present in crude glycerin are sulfur
(present in the waste cooking oil), potassium/sodium cations
(from either the potassium or sodium hydroxide base used as
catalyst in biodiesel manufacture), free fatty acids (present in
the cooking oil from animal-fat-based oil), and methanol (reacts
with the oil and replaces the glycerin to form biodiesel).21 NaCl,
NaOH, and C3H3OH were used to contaminate reagent-grade
glycerin and determine their effects on the reforming process.
The contaminants were introduced at a concentration of 0.5%
(21) Van Gerpen, J.; Shanks, B.; Pruszko, R.x; Clements, D.; Knothe,
G. Biodiesel Production Technology. Subcontract No. ACO-2-35016.
National Renewable Energy Laboratory, Golden, CO. http://www.nrel.gov/
docs/fy04osti/36244.pdf (accessed Aug 2006).

3504 Energy & Fuels, Vol. 21, No. 6, 2007

Douette et al.

Figure 6. Hydrogen yield calculated from successive GC samples taken every 35 min with the reformer operating at condition 12.
Table 5. Results of Analysis of Crude Glycerin Obtained from
Pacific Biodiesel

rapid increases in system pressure due to coke and deposit

formation and associated higher methane yield.

Proximate Analysis (% dry basis)

ash
volatile matter
fixed carbon

Conclusions
1.20
96.57
2.23

Heating Value (MJ/kg)

28.8

Ultimate Analysis (% dry basis)

C
H
N
S
Ash
O (by diff)

58.20
10.58
0.19
0.01
1.20
29.82

Ash Components (% of fuel, dry basis)

Si
Al
Ti
Fe
Ca
Mg
Na
K
P

0.0065
0.0141
<0.0001
0.0022
0.0012
0.0008
0.0062
0.5445
0.0037
Metals (mg/kg fuel)
As
B
Cd
Pb
Mn
Hg
Mo
Se
Zn

0.0204
<0.4
<0.06
<0.6
0.2398
<0.0001
<0.06
<0.01
0.0177

by weight. It was found that methanol had no effect on the

process but that the compounds containing sodium both caused

A statistical approach to study and improve the reforming of

glycerin to produce hydrogen was undertaken with the goal in
mind to reform crude glycerin obtained from the production of
biodiesel. Using a fixed bed reactor of nickel-based catalyst and
a 23 factorial design, the effects of the reformer temperature,
oxygen to carbon ratio, and steam to carbon ratio were studied
and quantified. Over the range of conditions tested, the oxygen
to carbon ratio was found to have the greatest effect. The greatest
hydrogen yield, 4.6 mol H2/mol glycerin, was obtained with an
oxygen to carbon ratio of 0, a steam to carbon ratio of 2.2, and
a reformer internal temperature of 760 C. This yield was 65%
of the stoichiometric maximum (7 mol H2/mol glycerin) and
85% of the theoretical maximum based on chemical equilibrium
(5.4 mol H2/mol glycerin). A secondary water gas shift reactor
was subsequently added downstream of the reformer to convert
carbon monoxide to hydrogen. A H2 yield of 5.3 mol/mol
glycerin was produced by operating the water gas shift reactor
at 369 C. The overall system error for all test conditions was
below 10%.
Crude glycerin was tested in the reformer, and initial results
were very close to that of reagent-grade glycerin, but the
hydrogen yield quickly decreased due to catalyst deactivation
and coking and deposit formation in the reformer. Analysis of
the crude glycerin sample showed N, S, and K to be present at
concentrations of 0.19, 0.01, and 0.5% (mass). Tests conducted
with reagent-grade glycerin doped with potential contaminants,
methanol, NaOH, and NaCl, indicated that Na was one of the
elements responsible for the reduced performance.
Acknowledgment. This research was sponsored in part by the
Office of Naval Research, under grant numbers N00014-01-1-0928,
N00014-04-1-0682, and N00014-06-1-0086.
EF060379W