SANDIA REPORT

SAND2008-0213
Unlimited Release
Printed January 2008

Final Report on LDRD Project:

Biodiesel Production from Vegetable Oils
Using Slit-Channel Reactors
Ken S. Chen and E. Eric Kalu

Prepared by
Sandia National Laboratories
Albuquerque, New Mexico 87185 and Livermore, California 94550
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SAND2008-0213
Unlimited Release
Printed January 2008

Final Report on LDRD Project:

Biodiesel Production from Vegetable Oils
Using Slit-Channel Reactors
Ken S. Chen
Nanoscale & Reactive Processes Dept.
Sandia National Laboratories
P.O. Box 5800
Albuquerque, New Mexico 87185-0836
E. Eric Kalu
Department of Chemical & Biomedical Engineering
FAMU-FSU College of Engineering
2525 Pottsdamer St.
Tallahassee, FL 32310

Abstract
This report documents work done for a late-start LDRD project, which was carried out during the
last quarter of FY07. The objective of this project was to experimentally explore the feasibility of
converting vegetable (e.g., soybean) oils to biodiesel by employing slit-channel reactors and
solid catalysts. We first designed and fabricated several slit-channel reactors with varying
channel depths, and employed them to investigate the improved performance of slit-channel
reactors over traditional batch reactors using a NaOH liquid catalyst. We then evaluated the
effectiveness of several solid catalysts, including CaO, ZnO, MgO, ZrO2, calcium gluconate, and
heteropolyacid or HPA (Cs2.5H0.5PW12O40), for catalyzing the soybean oil-to-biodiesel
transesterification reaction. We found that the slit-channel reactor performance improves as
channel depth decreases, as expected; and the conversion efficiency of a slit-channel reactor is
significantly higher when its channel is very shallow. We further confirmed CaO as having the
highest catalytic activity among the solid caralysts tested, and we demonstrated for the first time
calcium gluconate as a promising solid catalyst for converting soybean oil to biodiesel, based on
our preliminary batch-mode conversion experiments.
3

ACKNOWLEDGMENTS
This work was funded by the Laboratory Directed Research and Development (LDRD) program at Sandia
National Laboratories. We would like to thank Marianne Walck (6760), Grant Heffelfinger (8330), and
Joel S. Lash (1516) for programmatic support. We would also like to thank the following people:
Ben Wu (8125) for helpful technical discussions on vegetable oil-to-biodiesel conversion, Henry Romero
(24331) for assistance on the slit-channel reactor fabrication, Michael Kent (8332) for providing the
laboratory space and auxiliary facilities for carrying out the soybean oil-to-biodiesel experiments, and Ted
Borek (1822) and Sarah McIntyre (1816) for performing analytical analyses to determine percent
conversion of soybean oil to biodiesel.

CONTENTS
1. Introduction................................................................................................................................ 7
2. Slit-Channel Reactor Fabrication, Biodiesel-Production System Setup, and Conversion
Quantification ............................................................................................................................... 11
3. Results and Discussion ............................................................................................................ 14
3.1 Baseline Performance Batch Experiments..................................................................... 14
3.2 Baseline Performance Slit-Channel Reactors ................................................................ 14
3.3 Effect of Channel Depth on Fractional Conversion.......................................................... 16
3.4 Effect of Solid Catalyst..................................................................................................... 17
3.4.1 Qualitative results................................................................................................ 17
3.4.2 Quantitative results.............................................................................................. 19
3.4.3 Comparison of solid catalysts with NaOH liquid catalyst .................................. 20
4. Summary and Concluding Remarks ........................................................................................ 22
5. References................................................................................................................................ 23
Distribution ................................................................................................................................... 25

( This page is intentionally left blank )

1. INTRODUCTION
Worldwide petroleum-based energy resources are being depleted onshore crude oil production
peaked decades ago but our demands for petroleum are still going up. The United States
continued dependency on imported petroleum, particularly from the Middle East, has become an
important national security issue. Competition for global energy supply from emerging economic
powers such as China and India has added to the urgency for searching and developing
alternative energy sources that help us reduce our dependency on imported oil. Lastly,
environmental concerns such as pollution and global climate changes provide further motivation
to address the energy challenge that we face today1,2.
Biofuels, which are fuels derived from biomass such as corn, soybeans, sunflowers, algae, wood
chips, etc., are ideally suited for meeting the future energy challenges because they do not add to
global climate changes. This is attributed to the fact that plants use CO2 to grow during the
photosynthesis process; consequently, the CO2 formed during combustion of biofuels is balanced
by that absorbed during the annual growth of plants used as the biomass feedstock. Another key
advantage of biofuels over other alternative energy sources is that they can be burned (either
alone or mixed with petroleum-derived gasoline) in existing internal combustion engines.
Moreover, we can utilize current infrastructure such as pipelines, delivery trucks, and fueling
stations to transport and distribute biofuels3.
In the present work, we focused on the production of biodiesel (which is an important biofuel)
from vegetable (e.g., soybean) oils. With the conventional technology, vegetable oil mixed with
alcohol (e.g., methanol) reacts in large-scale batch reactors and in the presence of an alkaline
liquid catalyst (e.g., NaOH or KOH) to form methyl esters or biodiesel and glycerol or glycerine.
The transesterification reaction can take up to 12 hours or longer to complete; and at the end of
the reaction, it is necessary to use an acid to neutralize the liquid catalyst and to separate
biodiesel and glycerol from the product mixture. The catalyst-neutralization and productseparation steps are time-consuming, tedious, and costly. Readers who are interested in more
detailed discussions on the technical aspects of biodiesel production by transterification are
referred to a recent review provided by Meher et al.4. Apart from the increased costs in their
separation and recovery after the transesterification reaction, the alkaline catalysts are corrosive
to the equipment and will readily react with free fatty acids to form soaps, an undesired by-

product. It is therefore of interest to explore alternative approaches to the production of biodiesel

from vegetable oils, which can raise production efficiency and lower production costs.
One important alternative is to use solid catalysts, which do not require neutralization and can be
separated and recovered readily after the transesterification reaction is carried out. Several
reports have recently appeared in the literature on the production of biodiesel with solid
catalysts5-10. Some solid metal oxides such as those of zinc, magnesium, tin, etc. are known
catalysts for transesterification of vegetable oils to biodiesel. Unfortunately, some of the metal
oxide catalysts act according to an alternative homogeneous liquid-phase reaction mechanism
with subsequent production of unwanted soaps. Peter et al.5 investigated the use of solid zincarginate precipitated on carriers manufactured from silicium oxides. About 80% ester yield was
achieved within 20 minutes. They carried out their experiments at 125oC. Chai et al.6 used a
hetero-polyacid solid catalyst having activity that was not affected by the presence of free fatty
acids. A new continuous process utilizing a mixed oxide of zinc and aluminum as catalyst for the
production of biodiesel was recently commissioned in France10. It was reported that the catalyst
section utilizes two fixed bed reactors for the transesterification reaction, which is carried out at
an elevated temperature and pressure. It was further reported that the product does not need
elaborate cleaning as used in the homogeneous liquid-phase catalysis.
Another key alternative is to employ continuous channel reactors instead of batch reactors in the
production of biodiesel from vegetable oils operating in the continuous production mode can
raise production throughput. Moreover, species-diffusion paths can be significantly reduced,
particularly when the channel is very shallow, so as to create efficient mixing and thus result in
fast reaction. Though very few technical details were given, Oregon State University (OSU)
recently issued a news release titled Tiny Microreactor for Biodiesel Production Could Aid
Farmers, Nation, which reports the development of a micro-reactor for manufacturing biodiesel
from vegetable oils11. This technological development was based on the M.S. thesis work by AlDhubabian12, which was completed almost a year prior to the news release. In Al-Dhubabians
M.S. thesis work, two micro-reactors with channel length of 2.33 cm, channel width of 1.05 cm,
and channel depth of 100 mm and 200 mm, respectively, were fabricated and used to convert
soybean oil to biodiesel. Shortly after OSUs news release, the University of Texas at Arlington
also issued a news release titled Microreactor Process Developed for Biodiesel Refining,

which trumpets the development of a micro-reactor for processing biodiesel fuel13. Similar to
OSUs news release, very few technical details were given in UT Arlingtons news release,
which is understandable from the standpoint of protecting intellectual property. Fortunately, a
conference

paper

entitled

Inverse

Determination

of

Kinetic

Rate

Constants

for

Transesterfication of Vegetable Oils was published most recently by the UT Arlington group
led by Prof. Brian Dennis, which provides a glimpse into their experimental and modeling
efforts14.
One drawback in using micro-reactors for converting vegetable oils to biodiesel is that even
though the oil-to-biodiesel conversion efficiency may be high, the production throughput is low
since the length and width of a micro-reactor are limited to a few centimeters or less (due to the
limitations of the micro-fabrication technology used to make the micro-channel) as demonstrated
by the research group at OSU led by Prof. Goran Jovanovic and that at UT Arlington.
Consequently, the total area of surfaces that can serve as sites for carrying out the
transesterification reaction is very small. Another drawback with micro-reactors is that because
they are made by microfabrication technology, the manufacturing cost is high. To overcome
these two drawbacks, in the present work we employed slit-channel reactors instead of microreactors; the channel of a slit-channel reactor can be made by simple machining such that its
length and width are limited only by the mechanical strength of the material used instead of the
fabrication technology. Thus, the total surface area available for carrying out the
transesterification reaction in a slit-channel reactor can be several orders of magnitude higher
than that in a micro-reactor. Another important advantage using slit-channel reactors over microreactors is that manufacturing cost is significantly lower. The easy machining and associated low
cost make it possible to employ slit-channel reactors to convert vegetable oils (spent or fresh
ones) on small farms, and in homes and restaurants. It should be pointed out, however, that the
channel in a slit-channel reactor is deeper than that in a micro-reactor due to limitations in simple
machining. This means that for the same residence time the conversion efficiency using a slitchannel will be lower than that with a micro-reactor.
The ultimate goal is to employ slit-channel reactors having a solid catalyst (or catalysts) coated
on the channel surfaces so as to eliminate the need for catalyst neutralization and recovery. Due
to time and resource constraints, we didnt attempt to reach the ultimate goal in this project.

Instead, in the present work we fabricated four slit-channel reactors with varying channel depths
and conducted exploratory experiments that examined the effects of channel depth on percent or
fractional conversion of soybean oil to biodiesel and the effectiveness of six different solid
catalysts on catalyzing the soybean oil-to-biodiesel transesterification reaction.
This report is organized as follows. In Chapter 2, slit-channel reactor fabrication, biodieselproduction system setup, and percent-conversion quantification are described. In Chapter 3,
results from our exploratory experimental studies are presented and discussed. Lastly, in Chapter
4, a summary of the present work is provided along with recommendations on future efforts.

10

2. SLIT-CHANNEL REACTOR FABRICATION, BIODIESEL-PRODUCTION

SYSTEM SETUP, AND CONVERSION QUANTIFICATION
Four slit-channel reactors with channel depths of 1 mm, 2 mm, 5 mm, and 10 mm, respectively,
were fabricated. All four slit-channel reactors have a channel width of 2 mm and a channel length
of 15.24 cm. The bottom block of the four reactors was made of nylon and the top block of
transparent polycarbonate, which made possible to visualize the flows of soybean oil and the
methanol/NaOH solution through the channels. As shown in Figures 1 and 2, soybean oil was
introduced through the supply port in the bottom nylon block or plate whereas the homogeneous
methanol/NaOH solution was introduced through the supply port in the top polycarbonate plate.
The product mixture was collected from the outlet port in the bottom plate. As shown in Figure
1, a neoprene gasket was used to separate and at the same time seal the two parallel blocks that
form the slit-channel reactor.
A representative biodiesel-production system set up is shown in Figure 3. Here soybean oil and
methanol/NaOH solution were supplied to the slit-channel reactor via two Pulsatron (E-Plus
Series) precision pumps manufactured by Pulsafeeder (Punta Gorda, FL). The slit-reactor was
heated using a VWR Shaker Bath (Model 1217) manufactured by VMR International.
Methanol/NaOH solution supply port
Top block made of polycarbonate
Neoprene seal gasket

Soybean oil supply port

Bottom block
made of nylon

Product mixture collection port

Figure 1: An unassembled slit-channel reactor
11

Soybean oil supply tubing

Top polycarbonate block

Product mixture collection tubing

Methanol/NaOH solution supply tubing

Figure 2: An assembled slit-channel reactor

Methanol/NaOH supply pump

Soybean oil supply pump

Biodiesel product

Heating bath

Slit-channel reactor
Figure 3: Biodiesel-production system setup

12

Figure 4. Sample 1H NMR spectra

Fractional conversion of soybean oil to biodiesel was quantified using 1H NMR analysis and a
Bruker AC300 NMR spectrometer operating at 7.05 Tesla. Pw90 (pulse angle = 90 ) was 8 sec
with an equilibrium delay of 10 seconds. To calculate the fractional conversion, we followed the
approaches of Gelbard et al.18

and Knothe19. Although both methods involve the -CH2

(methylene) protons in the numerator of the conversion equations, a slight difference exists
between the two approaches. Whereas the Gelbard approach involves calculating the ratio of the
-CH2 (methylene) protons adjacent to the triglycerides ester (glyceryl) protons to the methoxy
protons of the methyl ester product, Knothe's approach uses the ratio of -CH2 (methylene)
protons to the sum of the methyl ester protons and the glyceryl protons. The chemical shifts of
the 1H NMR signals of the -CH2 (methylene) protons of the soybean oil resonate at (1H) = 2.2
2.4 ppm whereas the methoxy group of the methyl ester resonate around (1H) = 3.5 3.7 ppm.
Hence, for the Gelbard approach we used Eq. 1 below to calculate the fractional conversion:

2I M
3I A
and for Knothe's approach the following formula (Eq. 2) was used:
Fractional Conversion =

Fractional Conversion =

4I M
4I M + 9I G

(1)

(2)

where IM is the integration of the methyl ester protons, IA is the integration of the methylene
protons and IG is the integration of the glyceryl protons. The numbers used to multiply the
integration factors signify the number of protons involved in the group or environment. As an
illustration of the approaches, the sample spectra as displayed in Figure 4 shows that at ~ 4.1
ppm, IG = 0.941, at 3.6 ppm, IM = 25.055 and between 2.1 2.3 ppm, IA = 18.105. Thus, using
Equations 1 and 2 Gelbards and Knothe's approaches yield 0.923 and 0.922, respectively.
13

3. RESULTS AND DISCUSSION*

3.1 Baseline Performance Batch Experiments
Several experiments were conducted to verify the appropriate methanol to oil ratio to use, the
amount of NaOH catalyst required for ester conversion and the exploration of residence time
effects at different reaction temperatures etc.

Based on the results of such investigations, some

experimental parameter values were chosen. Table 1 summarizes the batch experimental
parameters of this work. Several baseline data are qualitative in nature. For instance, the
conditions under which the reactor product gels. Such data have not been included in this report.
Table 1: Batch Experimental Parameters
Variable or parameter

Range of values used

NaOH catalyst

0.0263 g/ml of methanol

Temperature

55oC or 60oC or 65o C or room temperature

Methanol:Oil molar ratio

6:1 (equivalent volume ratio 1:4)

Stirring rate

120 -200 rpm

The effect of residence time on the conversion of triglycerides from soybean oil to ester or
biodiesel with NaOH liquid catalyst at a temperature of 65o C is shown in Figure 5. The result
shows that with NaOH as a catalyst, about 70% triglyceride conversion can be achieved in one
hour. The data point at 15 minutes, which shows exceptionally high fractional conversion, is
most likely an outlier that was caused by uncertainty in NMR analysis or incorrect methanol to
oil ratio being used. Noureddini and Zhu15 made similar observations with a highly stirred batch
system. Other published literature data for well mixed and stirred batch reactors support the
results obtained in this work16. As has been pointed out in the literature, both temperature of
reaction and mixing intensity affect the triglyceride conversion15. Thus, the results shown in
Figure 5 are unique for the operating conditions employed in the present work.

3.2 Baseline Performance Slit-Channel Reactors

The motivation for the use of a slit-channel reactor is to obtain improved oil to biodiesel
conversion and ultimately develop a solid catalyst that can be utilized in the slit-channel reactor
*

Based on results/discussions presented in the project report submitted to Sandia by E. Eric Kalu on Nov. 15, 2007.

14

Fractional Conversion

1.0
0.8
0.6
0.4
0.2
0.0
0

10

20

30

40

50

60

70

80

Time (min)
Fig. 3: Triglycerides conversion in a batch reactor with
Figure 5. Fractional conversion of soybean oil toobiodiesel in a batch reactor
homogeneous NaOH catalyst at 65 C
with homogeneous NaOH liquid catalyst at 65 C.

so as to increase production throughput and lower production costs in biodiesel production. In

order to demonstrate the superior performance of slit-channel reactors over batch reactors, NaOH
liquid catalyst was used to obtain fractional conversion data in the slit-channel reactor. In Figure
6, fractional conversion for biodiesel in a 2 mm slit-channel reactor is compared to that in a batch
reactor (which also employed liquid NaOH as catalyst). It is to be noted that the performance (in
terms of fraction conversion) of the slit-channel reactor is dependent on the channel depth as
shown later in this report. Performance of slit-channel reactors with deeper channels approach
that of batch reactors; hence, slit-channel reactors are less efficient than those with shallow
channels. Thus, the fractional conversion improvement shown by the 2 mm channel depth over
the batch reactor supports the core assumption of the present work (which is that a slit-channel
reactor is more efficient in converting soybean oil to biodiesel due to more efficient mixing and
thus faster reaction). Furthermore, the improved performance of the slit-channel reactor is
irrespective of its lower temperature (55o C) of operation over the batch system (65oC). 1H NMR
solution state analysis was used to analyze and determine the conversion of soybean-oil
triglyceride to biodiesel

16-19

. The ratio of the area of the spectra of the methylene protons

15

adjacent to the triglyceride ester group to the area of the spectra of the methoxy protons of the
methyl ester product is used for the calculation of the conversion values reported. The details of
the 1H NMR method has been provided previously in Chapter 2.

fractional conversion

1.00
0.80
0.60
0.40
mm channel,
channel, 55
oCC
22mm
55
oCC
reactor, 65
Batch reactor,
Batch
65

0.20
0.00
0

10

20

30

40

50

60

70

Mean residence-time (min)

6. Performance
comparison
slit-channel improvement
reactor with batch
reactor:
Fig.Figure
4: Slit-channel
reactor
fractionalofconversion
over
batch reactor
fractional conversion

3.3 Effect of Channel Depth on Fractional Conversion

The channel depth affects the mode of interaction between reacting species and hence the
conversion. It is accepted that a high surface-to-volume ratio, short diffusion distances, fast and
efficient heat dissipation and mass transfer enable miniaturized chemical processes to exhibit
significant advantages over conventional techniques. Consequently, one would expect the four
channel reactors to show individual unique characteristics. In Figure 7, a comparison is made to
demonstrate fractional conversion improvement in the slit-channel conversion operation as the
channel depth is decreased. As expected, the 1 mm channel shows the greatest improvement.
However, the experimental data for the 10 mm and 5 mm channels do not follow the expected
trend. The reason for this observation is not clear at this point but could be attributable to several
sources of experimental errors including not having exact methanol to oil ratio at all

16

experimental data points. The importance of the data however should be clear when we compare
the 1 mm channel to the 2 mm channel. It is evident in support of the thesis that decreasing the
channel depth results in the improvement in conversion efficiency.

fractional Conversion

1.00
0.80
0.60
1 mm channel depth
2 mm channel depth
5 mm channel depth
10 mm channel depth

0.40
0.20
0.00
0.0

2.0

4.0

6.0

8.0

10.0

12.0

14.0

Mean residence-time (min)

Fig.7.5:Effect
Slit-channel
depthdepth
effects
conversion
Figure
of slit-channel
on on
fractional
conversion

3.4 Effect of Solid Catalyst

3.4.1 Qualitative results

In reporting our work under the solid catalyst, both qualitative and quantitative aspects of data
collected will be referenced. Initially, we used and evaluated the solid oxides of zinc (ZnO),
zirconium (ZrO2), magnesium (MgO) and calcium (CaO) as supplied. After more than 3.5 hours
at 65oC, the CaO showed best evidence of activity followed by ZnO. Based on this result, it was
concluded that as the supplied oxides need some form of activation (thermal or otherwise) to
stimulate them into activity. Further, the order of activity of the oxides (as supplied) was
classified as follows:
ZrO2 < MgO < ZnO < CaO

17

Since ZnO and CaO showed some activity towards biodiesel production, we considered the
combination of the two for synergistic activities. Three methods of combination were examined
as follows:
(a) A mixture of CaO and ZnO in the ratio 1:2 by weight and used as prepared.
(b) A mixture as in (a) but heated up to or greater than 600oC.
(c) Mix Zn(OH)2 with CaO and heat mixture together at more than 900oC for
between 8 - 24 hours.
The Zn(OH)2 was prepared as follows: 0.69 g ZnCl2 was dissolved in 28 ml water. Ammonia
was added in the solution to precipitate Zn(OH)2. The excess water was decanted and precipitate
washed several times before mixing the precipitate with 1 gm CaO. The mixture was then heated
to the required temperature and time.
Table 2: Identity of Calcium-Zinc Based Catalysts
Sample Identity

Active Components

Thermal Activation Method

33.3 wt % CaO + 66.7 wt % ZnO

No thermal treatment

33.3 wt % CaO + 66.7 wt % ZnO

Heated to 600oC for 8 hr

Zn(OH)2 mixed with CaO

Heated at at 900oC for 24 hr

Following the activities described above, qualitative observation shows that the activity of
catalyst A was not better than that of CaO alone. Catalyst B showed results better than those of
catalyst A. The best result was obtained from catalyst C. Unfortunately, the Sandia analytical
services could not analyze the samples for us for quantitative comparison of the conversion
values achieved by these catalysts.
Significance of the Qualitative Studies
The significant milestone of the qualitative studies above is the development of a systematic
method of using CaO as a catalyst for biodiesel production. We learned that the catalytic activity
of as supplied CaO can be improved by annealing at 300oC or higher (the higher the temperature
the better the catalyst performance) for some hours. It was also demonstrated that the synergy
between the combination of Zn(OH)2 with CaO can yield a better performing solid catalyst.

18

Conversion

Conversion

0.58
0.56
0.54
0.52
0.50
0.48

20

40

60

80

100 120 140

0.50
0.48
0.46
0.44
0.42
0.40

20

40

Time (minutes)
Conversion

Conversion

0.5
0.4
0.3
20

40

60

80

80

100 120

Time (min)

0.7
0.6

60

100

120

1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3

200

400

600

800

1000

Time (min)

Time (min)

Fig. 6: Conversion time curve for solid Catalysts:

Figure 8. Conversion vs. time for solid catalysts:
A: CaO (300 oA:
C,CaO
5 hr,
0.15
B: HPA
(600 o C, 5 hr, 0.15 g),
(300
C, g)
5 hours,
0.15 g);
(600 C, 5 hours, 0.15 g);
C: HPA (560 oB:C,HPA
5 hr,
0.14 g), D: Calcium gluconate (275 oC, 3hr, 0.15 g)
C: HPA (560 C, 5 hours, 0.14 g);
D: Calcium gluconate (275 C, 3 hours, 0.15 g);

3.4.2 Quantitative results

Having determined that CaO is a promising solid catalyst, we evaluated other promising catalysts
and combinations thereof. Based on the recent report of Chai et al.6 , we evaluated
heteropolyacid (HPA) Cs2.5H0.5PW12O40 as a catalyst. In addition to these two, we also evaluated
Calcium gluconate (unlike other catalysts, this is an environmentally friendly catalyst). For the
preparation of HPA, the method described in the literature was followed (see Ref. 6). On
annealing, however, we observed that the color of the crystals tended to depend on the annealing
temperature. For instance at 560oC, white crystalline salt was obtained while greenish salt
resulted at 600oC. The salt that resulted at 300oC annealing was darkish blue. In all cases, the
transesterification process produced whitish/milky color when the salt came into contact with
methanol. Figure 8 shows conversion time curves for the solid catalysts.

19

3.4.3 Comparison of solid catalysts with NaOH liquid catalyst

The ultimate objective of our research effort is investigating the feasibility of a solid catalyst
soybean oil transesterification in a biodiesel slit-channel reactor and the best method of coating
the channel with the solid catalyst. We compared the performance of the solid catalysts to the
homogeneous NaOH liquid catalyst by following the fractional conversion of triglycerides as a
function of time in the presence of the different catalysts. The results obtained are shown in
Figure 9.
All the solid catalysts used in Fig. 9 were annealed at 300 oC for 3 hours. The important
deduction to make from the figure is that none of the solid catalysts showed catalytic activity
comparable to that of homogeneous NaOH catalyst. Also, we observe that both the HPA and
gluconate have high catalytic activity especially at the early stage of the transesterification
process. Whereas the calcium gluconate tended to sustain its high activity, the HPA activity was
not sustained for the duration of the time reported.

Fractional Conversion

1.0
0.8
0.6
0.4
NaOH
NaOH
CaO
CaO
Calcium gluco
gluconate
Calcium
nat e
CsHPA
2.5P W

0.2
0.0
0

50

100

150

Time (min)
Fig. 7: Batchwise Conversion of soybean oil to biodiesel with different catalysts

Figure 9. Batchwise conversion of soybean oil to biodiesel with different catalysts

20

For the soybean-oil-to-biodiesel experiments to be carried out in slit-channel reactors, we need a

method to coat a selected solid catalyst (e.g., Calcium gluconate, CaO or HPA) on the channel
surfaces. For the present work, we assessed the HPA mixed with cellulose. After undergoing
thermal annealing, the cellulose-HPA mixture was weighed and added in a batch oil/methanol
mixture. The results obtained were similar to those obtained in the absence of cellulose.
However, more detailed experiments are required before a firm conclusion can be reached.
In addition to supporting the qualitative results, the quantitative data show that calcium gluconate
is a very promising heterogeneous catalyst. Although limited in scope, preliminary data of solid
catalyst mixed with polymer show promise of an approach for coating of the surface of the slitchannel reactors.

21

4. SUMMARY AND CONCLUDING REMARKS

Four slit-channel reactors with varying channel depth were fabricated and used to conduct
exploratory experiments on converting soybean oil to biodiesel. We successfully produced
biodiesel with different degree of conversion using the four slit-channel reactors fabricated.
Results obtained from our exploratory experiments show that the slit-channel reactor
performance (in terms of percent conversion) depends on the channel depth lower channel
depths perform better than channels that are deeper; that is, percent conversion of soybean oil to
biodiesel increases with decreasing channel depth, as expected, due to more efficient mixing and
and thus faster reaction as the channel becomes more shallow.
Six solid catalysts (CaO, MgO, ZnO, ZrO2, calcium gluconate, and heteropolyacid or HPA) were
evaluated for their effectiveness in soybean oil transesterification using batch reactors. Amongst
these, CaO was confirmed as having the highest activity in catalyzing the transesterification
reaction whereas calcium gluconate was demonstrated for the first time as a promising solid
catalyst in our exploratory experiments using batch reactors.
In the present work, due to time and resource constraints, we didnt attempt to couple slitchannel reactors with solid catalysts in converting soybean oil to biodiesel. To realize the great
potential of slit-channel reactors, however, the coating of the surfaces of the slit-channel reactor
with a solid catalyst (or catalysts) needs to be investigated. Such a study will reveal any shortcomings of coated solid catalyst over its performance in batch mode uncoated. A critical aspect
of further research is the solid-catalyst deposition on the channel surfaces of a slit-channel
reactor. Optimization of thermal treatment temperature for the solid catalysts also need to be
investigated. Lastly, a predictive mathematical model of the slit-channel reactor needs to be
developed; such a model, after being validated, can be exercised to reduce the number of
experiments needed to study and understand the non-batch mode transesterification process.

22

5. REFERENCES
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8. I. K. Mbaraka and B. H. Shanks, Conversion of oils and fats using advanced mesoporous
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M. S. Thesis, Oregon State University (2005).

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13. News release, University of Texas at Arlington, June 5, 2006, UT Arlington Office of Public
Affairs. http://www.uta.edu/public-affairs/pressreleases/page.php?id=1729.
14. B. H. Dennis, W. Jin, and R. B. Timmons, Inverse determination of kinetic rate constants
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Design and Optimization Symposium, Miami, Florida, USA, April 16 18, 2007.
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1457 1463 (1997).
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489 493 (2000).

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1 Prof. E. Eric Kalu
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