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2012 International Transaction Journal of Engineering, Management, & Applied Sciences & Technologies.




                  International Transaction Journal of Engineering,
                  Management, & Applied Sciences & Technologies
                           http://TuEngr.com,                     http://go.to/Research




                          Parameters Analysis of the Assisted Combustion of
                          Residual Biodiesel Glycerol
                                                                        a*                                 a
                          Francisco S. Cavalcante Junior                     , José Cleiton S. Alves ,
                                                                    a                                  a
                          Francisco Sales A. Cavalcante , and Lutero C. de Lima
a
    Graduate Program on Applied Physics, State University of Ceará, BRAZIL

ARTICLEINFO                         A B S T RA C T
Article history:                             With the increased production of biodiesel, an excess of
Received 26 July 2012.              glycerol is being generated worldwide. One way to reduce the surplus of
Received in revised form
03 September 2012.                  glycerol would be to use it as low calorific fuel in the own process of
Accepted 12 September 2012.         biodiesel production. However, being a high viscosity fuel with also
Available online 14 September       high ignition point, its combustion requires severe control and
2012.                               monitoring due to the formation of the toxic pollutants. It is common
Keywords:                           practice mainly in developing countries to use biomass fuels in rural
Biodiesel;                          regions and it looks that with glycerol will not be different. The present
Glycerol;                           article had as objective the construction of a simple chamber for the LPG
Combustion.                         assisted combustion of the biodiesel residual glycerol and the evaluation
                                    of all parameters related to the combustion itself. At a fixed mass flow of
                                    LPG different mass flows of glycerol were burnt and parameters such as
                                    O2, CO, CO₂, NOx, exhaust gases temperature, combustion efficiency
                                    and excess air were measured.


                                      2012 International Transaction Journal of Engineering, Management, &
                                    Applied Sciences & Technologies.


1. Introduction 
       With the increase in world production of biodiesel, an excess of glycerol has being
generated and many biodiesel producers can no longer give a suitable destination for the huge
amount of produced glycerol. As consequence this brings not only reduction of price of
glycerol but also the concern about impacts caused by the discharge of glycerol to the
environment without adequate treatment (Fernando et al., 2007). Volumetrically, for every 10
* Corresponding author (Francisco S. Cavalcante Junior). Tel/Fax: +55-85-31019902. E-mail
address: juniornum@gmail.com       2012 International Transaction Journal of Engineering,
Management, & Applied Sciences & Technologies.       Volume 3 No.4         ISSN 2228-9860                      455
eISSN 1906-9642. Online Available at http://TuEngr.com/V03/455-465.pdf
liters of biodiesel produced, a liter of glycerol is generated as residue. Glycerol is a co-product
from the production of biodiesel and its chemical nomenclature is propane-1,2,3-triol, an
organic compound belonging to the family of alcohol. It is odorless, hygroscopic and viscous.
The glycerol with purity above 95% is also called glycerin and in its raw form has low
commercial value because it may contain residues of methanol, sodium hydroxide, fatty acids,
salts, sulfur and other contaminants (Barbosa, 2008).            It is used primarily in the food,
pharmaceutical and chemical industries. According to the National Petroleum Agency in 2008
Brazil has produced 1.17 billion liters of biodiesel. The production of glycerol was of about
117 million liters however in that year only 11 million liters was consumed by the Brazilian
market. As highlighted before many biodiesel producers are concerned about not knowing what
to do with the large amounts of glycerol produced. In the recent literature there are many
articles related to different applications of glycerol. To name a few, Arechederra et al. (2007)
performed experiments using glycerol as a source for a fuel cell. According to the researchers
there are some peculiar characteristics that make glycerol a good alternative for this application
because it is non-toxic, non-volatile, non-flammable at low temperatures, has high energy
density, and is abundant due to the fact that it is a byproduct of biodiesel production. Adhikari et
al. (2009) made a review of different generation methods, catalysts and operating conditions
used to produce hydrogen using glycerol as a substrate. They stressed that most of the studies
were focused on hydrogen production via steam reforming process and few work has been done
on producing hydrogen from crude glycerol.

    According to Bohon et al. (2011) one possible use for the excessive surplus of glycerol in
the market is to use it as a boiler fuel to produce steam and co-generate electricity and if
combined with biodiesel production, this has the added advantages of optimizing energy
integration, eliminating transportation costs, and displacing the need for fossil fuels. Striugas et
al. (2008) made analysis of combustion of emulsions of glycerol and heavy fuel oil. They made
comparison on emissions of NOx, SO2 and CO from the emulsions with the emissions of heavy
fuel oil and they found better indexes of emission for the emulsions. Still, according to Striugas
et al. (2008), it is difficult to atomize with conventional equipment because of its high density
and viscosity, which means that it must be heated in advance. In fact, glycerol has quite a high
auto-ignition temperature (370 °C) compared to other liquid fuels, so it flames up with
difficulty. Another consideration highlighted by Striugas et al. is that when glycerol is heated
around 280 °C, toxic acrolein is produced. They made research about the use of glycerol to

    456          Francisco S. C. Junior, José C. S. Alves, Francisco S. A. Cavalcante a, and L.C. de Lima
produce fuel emulsions containing heavy fuel oil. They observed that the burning of such
emulsions leads to the decrease in the emission of sulphur dioxide by up to six-fold less than the
concentration produced by burning pure heavy fuel oil. They observed too that the
concentration of NOx, CO, and SO₂ in the flue gases did not exceed the permissible levels of
pollutants emitted from fuel combustion plants, as specified in EU Council Directives.

     Patzer (2007) studied the combustion of mixture of glycerol and yellow grease in a
chamber without specific adaptations and according to the author the results for the mixture
presented better results than the combustion of raw glycerol. The same author stressed that it
was not possible to realize a stable process of combustion due to the peculiar characteristics of
raw glycerol as a fuel. Asavatesanupap and Santikunaporn (2010) presented a feasibility study
on the production of solid fuel from glycerol and agricultural wastes. They mixed ground crop
residues, dried durian shell and bagasse with glycerol from biodiesel in various weight ratios.
They concluded that solid fuel derived from either dried durian shell or bagasse and glycerol
can be used as an alternative fuel according to their energy contents even though amount of
acrolein is fairly excessive. Bohon et al. (2011) developed a system where the glycerol is
pressurized and injected into a combustion chamber. They reported a range of emissions
measurements, including nitrogen oxides, total hydrocarbons, and particle mass for two grades
of crude glycerol (methylated and demethylated) and compared these to No. 2 fuel oil and
propane. They concluded that a properly designed refractory burner can provide the thermal
environment to effectively combust glycerol, but that high particulate emissions due to residual
catalyst are likely to be an issue for crude glycerol combustion.

     Differently from all authors cited above, in the present article the combustion of raw
glycerol was made in a simply designed chamber in combination with LPG. In fact LPG was
the main fuel in the combustion and glycerol entered as an aggregate aiming to reduce the
consumption of LPG. Almost every possible parameters of combustion were evaluated.
Parameters such O2, CO, CO2, NOx, excess air, combustion efficiency and exhaust gases
temperature were measured. These measurements have presented an interesting aspectwhich is
the possibility to use raw glycerol as an energetic aggregate to the combustion of LPG
representing potentially reduction in the consumption of such important fuel.



* Corresponding author (Francisco S. Cavalcante Junior). Tel/Fax: +55-85-31019902. E-mail
address: juniornum@gmail.com       2012 International Transaction Journal of Engineering,
Management, & Applied Sciences & Technologies.       Volume 3 No.4         ISSN 2228-9860   457
eISSN 1906-9642. Online Available at http://TuEngr.com/V03/455-465.pdf
2. Material and Methods 
    Figure 1 shows a schematic diagram of chamber with accessories designed for the assisted
combustion of raw glycerol. The chamber dimensions is 0.75 m height, 0.60 m width and 0.60
m depth and the experimental setup consists of (1) a raw glycerol recipient, (2) valves for the
control of glycerol and LPG mass flows, (3) a stainless duct of 3.7 mm internal diameter, (4)
inlet to the flue gases analyser, (5) a chimney of 2.4 m length and 6.5 cm internal diameter, (6)
a commercial atmospheric LPG burner, (7) a LPG filter, and (8) a LPG tank.




                   Figure 1: Schematic diagram of the experimental setup.


    The LPG burner (Jackwal® - Brazil) with the nominal gas consumption of 0.19 kg/h                was
permitted to work until steady-state regime was reached and the oxygen concentration in the
flue gases was adjusted to 6.0%. The 6.0% of oxygen in the flue gases is an established criterion
in the literature in order to quantify the emission of pollutants in combustion processes
(Kuprianov et al., 2010).Raw glycerol at mass flows of 0.036, 0.072, .108 and 0.144 kg/h was
fed to the preheated combustion chamber through a stainless duct as shown in Fig. 1. The
glycerol feeding duct was maintained parallel and close to the head of the LPG burner in such a
way that it burned inside the LPG flame.


    The glycerol used was produced in the biodiesel plant in the State of Ceará – Brazil by the
Petrobrás Biofuels Company. Basically the biodiesel produced in such Company 20% is
derived from cotton and 80% is derived from soybeans. As provided by Petrobrás the glycerol
sample contains 81.8% glycerol, 9.8% water, 5.8% ash, and 2.6% organic material.

    458          Francisco S. C. Junior, José C. S. Alves, Francisco S. A. Cavalcante a, and L.C. de Lima
According to Metzger (2007) one kilogram of glycerol contains less chemical energy than
kerosene and gasoline. Glycerol has an average of 16 MJ per kilogram of chemical energy and
kerosene 42.8 MJ and gasoline 44.4 MJ.

    All combustion parameters were measured by the flue gases analyser TESTO 330-2 LL.
Such analyser has cells for the measurement of oxygen, carbon monoxide and nitrogen oxides.
It has also thermocouples for the measurement of the ambient and flue gases temperatures. As
provided by the manufacturer of such equipment the uncertainty for the measurement of O₂ is
±0.2%. For the measurement of temperature the uncertainty is ±0.5 °C and for the measurement
of the other parameters (CO₂, CO, and NOx) the uncertainty was of ±5%.


3. Results and Discussion 
     Figure 2 presents the oxygen concentration in the flue gases as a function of the glycerol
mass flow. As stressed before, the zero mass flow of glycerol corresponds to the situation where
only the LPG burner is working and the concentration of oxygen in the flue gases was fixed at
6.0%. For the glycerol mass flows of 36 to 108 g/h the oxygen concentration was in average
5.8% and for the mass flow of 144 g/h the oxygen concentration decreased to 5.3%.




         Figure 2: O₂ concentration in the flue gases for different glycerol mass flows

     Figure 3 presents the concentration of carbon monoxide as a function of the glycerol mass
flow. The percentage of CO increases with the increase in the glycerol mass flow. At zero flow
of glycerol and at the fixed percentage of oxygen 6.0% considered for the only combustion of
* Corresponding author (Francisco S. Cavalcante Junior). Tel/Fax: +55-85-31019902. E-mail
address: juniornum@gmail.com       2012 International Transaction Journal of Engineering,
Management, & Applied Sciences & Technologies.       Volume 3 No.4         ISSN 2228-9860   459
eISSN 1906-9642. Online Available at http://TuEngr.com/V03/455-465.pdf
LPG the CO concentration was of 15 ppm. It increased to 178 ppm at the glycerol mass flow of
144 g/h. Gonzalez et al. (2004) considered that this behavior is due to the fact that the furnace
temperature rises as the mass flow increases and this contributes to the endothermic reaction C
+ CO₂ ↔ 2CO. At the other hand, Kuprianov et al.(2010) consider that the CO emission
exhibits strong influences of both excess air and fuel quality comprehending carbon content and
moisture. In general CO decreases with the increase in the excess air. So the reason for the
increase of CO as a function of the increase in the glycerol mass flow is possibly due the carbon
content of the raw glycerol used since the level of moisture in all samples tested was the same.




          Figure 3: CO concentration in the flue gases for different glycerol mass flows.


    Figure 4 presents the temperature and the percentage of carbon dioxide in the flue gases for
all glycerol mass flows. It is observed that the percentage of CO₂ increases simultaneously with
the increases of the flue gases temperature and glycerol mass flow. This can be explained by the
fact that the combustion efficiency can be put as a function of the sensitive heat and not-burnt
gaseous losses of the fumes. However the sensitive heat is dependent on the flue gases CO₂
besides fumes and ambient temperature (Gonzales et al., 2004). As also it can be seen in
Figure 5 the combustion efficiency kept practically constant (around 83%) at the glycerol flows
tested.




    460           Francisco S. C. Junior, José C. S. Alves, Francisco S. A. Cavalcante a, and L.C. de Lima
Figure 4: CO₂ and flue gases temperature for different glycerol mass flows.

    Gonzalez et al. (2004) observed that fuel mass flow scarcely influences combustion
process efficiency, corroborating the finding of this study as depicted in Figure 5. Interestingly,
Miranda et al. (2007) didn’t reach the same conclusion when they studied combined
combustion of various phase of olive wastes in a conventional combustor under varying fuel
mixture and mass flows.




                  Figure 5: Combustion efficiency against glycerol mass flow.

     Figure 6 presents the excess air as a function of the glycerol mass flow. For the reference
condition where the only LPG combustion was maintained at 6.0% of oxygen in the flue gases
the excess air was of 44.8%. With the introduction of glycerol the excess air decreased to 33.7%
* Corresponding author (Francisco S. Cavalcante Junior). Tel/Fax: +55-85-31019902. E-mail
address: juniornum@gmail.com       2012 International Transaction Journal of Engineering,
Management, & Applied Sciences & Technologies.       Volume 3 No.4         ISSN 2228-9860   461
eISSN 1906-9642. Online Available at http://TuEngr.com/V03/455-465.pdf
at the mass flow of 144 g/h. This behavior is in some way expected since the more is the mass
flow of glycerol the more the oxygen needed for completing the combustion.




                    Figure 6: Excess air for different glycerol mass flow.

    In order to effectively quantify the emission of pollutants resulted from the assisted
combustion of raw glycerol the O₂ was fixed at 6.0% in dry basis and the values of CO and NOx
were measured for different mass flows of glycerol. As already shown in Fig. 2, for no flow of
glycerol and only burning LPG CO reached 15 ppm. This value reached 81 ppm for the flow of
36 g/h and increased to 178 ppm when the glycerol mass flow was 144 g/h. The same tendency
of CO emission was observed by other researchers. Miranda et al. (2007) measured CO under
the same basis (O₂ 6.0%) and found value of about 2000 ppm for the combustion of olive
kernel, 5000 ppm for the combustion of pulp and 2500 ppm for the combustion of residual olive
pomace. Kuprianov et al.(2010) also for the same condition found values of CO at 350 ppm
during the combustion of moisturized rice husk in a swirling fluidized-bed combustor. At other
hand, Madhiyanon et al. (2010) found for the same condition values at the range of 50 to 550
ppm depending on the bed temperature of the combustion of rice-husk in a short
combustion-chamber-chamber fluidized-bed combustor.

    Figure 7 presents the emission of NOx as a function of glycerol mass flows at the condition
of O₂ fixed at 6.0% for the flue gases under dry basis. For the condition of only burning LPG
the emitted NOx was 36 ppm. For almost all glycerol mass flows the NOx emissions were about
27 ppm. However at mass flow of 144 g/h the emission reached 29 ppm. Bohon et al. (2011)


    462         Francisco S. C. Junior, José C. S. Alves, Francisco S. A. Cavalcante a, and L.C. de Lima
found NOx emissions of 7 to 10 ppm for one of their prototype burner under the condition of
0% O₂ and of 160 to 240 ppm for other refractory-lined furnace. They considered differences in
burner swirl and excess air, as well as differences in compositions between pure glycerol and
actual crude glycerol wastes as the responsible. Miranda et al. (2007) found 50 to 120 ppm of
NOx emission for their combined combustion of olive combustor. Their emission increased
with the increase of the mass flow and flame temperature. Kuprianov et al. (2010) measured
NOx at about 170 ppm and reduced it to 128 ppm when the best combustion and emission
performance of the SFBC was achievable and when burning moisturized rice husk with
moisture content of 2-25%, at excess air of 40-50%. Madhiyanon et al. (2010) reached almost
the same range as Kuprianov et al. (2010) when they burned rice husk in SFB combustor.




              Figure 7: NOx emission at 6.0% O₂ for different glycerol mass flow


4. Conclusion 
     The LPG assisted combustion of different glycerol mass flows of raw glycerol in a simply
designed chamber was realized in this study. Although glycerol is not considered a
conventional fuel and presents many problems for its combustion, results in this study indicated
that it is possible to burn glycerol. The emission level of CO under the condition of 6.0% O₂ in
the flue gases (and in the literature established control condition for the measurements of CO
and NOx emissions) for different glycerol mass flows and constant LPG mass flow was
considered very high. However the emission of NOx under the same condition was quite low
when compared with published experiments of biomass combustion. The pressurized spray of
* Corresponding author (Francisco S. Cavalcante Junior). Tel/Fax: +55-85-31019902. E-mail
address: juniornum@gmail.com       2012 International Transaction Journal of Engineering,
Management, & Applied Sciences & Technologies.       Volume 3 No.4         ISSN 2228-9860   463
eISSN 1906-9642. Online Available at http://TuEngr.com/V03/455-465.pdf
glycerol, the formation of ash, particulate matters, and acrolein on the fumes are continued
problems for the combustion of glycerol. In the present time the authors of this article are
tackling such problems.


5. Acknowledgements 
    One of the authors (F.S.A. Cavalcante) thanks the Brazilian National Council for Scientific
and Technological Development (CNPq) for financial support.


6. References 
Fernando S., Adhikari S., Kota K.,Bandi R. (2007). Glycerol base automotive fuels from future
      biorefineries.Fuel, 86, 2806-9.

Barbosa C.R. (2008). Evaluation of glycerol derived from biodiesel production as substrate for
      endotoxins production by Bacillus thuringiensis var. israelensis.Dissertation (Master of
      Science in Industrial Biotechnology) - Engineering School of Lorena, University of São
      Paulo, Lorena, São Paulo.

Agência Nacional do Petróleo, Gás Natural e Biocombustíveis (ANP). Dados Estatísticos
      Mensais(In                                                        Portuguese).
      Avaialableat<http://www.anp.gov.br/?pg=56046&m=&t1=&t2=&t3=&t4=&ar=&ps=
      &cachebust=1312202333159> (accessed August 2011).

Arechederra R.L., Treu B.L., Minteer S.D. (2007). Development of glycerol/O₂ biofuel
      cell.Journal of Power Sources, 173, 156-161.

Adhikari S., Fernando S.D., Haryanto A. (2009). Hydrogen production from glycerol: an
      update. Energy Conversion and Management, 50, 2600-4.

Bohon MD, Metzger BA, Linak WP, King CJ, Roberts WL. Glycerol combustion and
      emissions.Proceedings of the Combustion Institute, 33, 2717-24.

Striugas N., Šlančiauskas A., Makarevičienė V., Gumbytė M., Janulis P. (2008). Processing of
       the glycerol fraction from biodiesel production plants to provide new fuels for heat
       generation.Energetika. 54, 5-12.

Patzer R., Norris M., Doering A., Jorgenson R.,Neece C. (2007).Emissions evaluation:
       Combustion of crude glycerin and yellow grease in an industrial fire tube boiler.
       Agricultural      Utilization       Research     Institute,     available      at
       <http://www.auri.org/research/glycerin%20report%20final.pdf> (accessed November
       2010).

Asavatesanupap C., Santikunaporn M.A. (2010). Feasibility study on production of solid fuel
      from glycerol and agricultural wastes.International Transaction Journal of
      Engineering, Management, & Applied Sciences & Technologies, 01, 43-51.


    464         Francisco S. C. Junior, José C. S. Alves, Francisco S. A. Cavalcante a, and L.C. de Lima
Kuprianov V.I., Kaewklum R., Sirisomboon K., Arromdee P., Chakritthakul S. (2010).
      Combustion and emission characteristics of a swirling fluidized-bed combustor burning
      moisturized rice husk. Appl. Energy. 87, 2899-2906.

Metzger, B. Glycerol Combustion, Master Thesis, North Carolina State University, Raleigh, North
      Carolina, 2007.

Gonzalez J.F., Gonzalez-Garcia C.M., Ramiro A., Gonzalez J.,Sabio E., Ganan J., Rodriguez
      M.A. (2004). Combustion optimisation of biomass residue pellets for domestic heating
      with a mural boiler. Biomass and Bioenergy, 27, 145-154.

Miranda M.T., Cabanillas A., Rojas S., Montero I., Ruiz A. Combined combustion of various
      phases of olive wastes in a conventional combustor. Fuel, 86, 367-372.

Madhiyanon T, Sathitruangsak P, Soponronnarit S. Combustion characteristics of rice-husk in a
      short-combustion-chamber fluidized-bed combustor (SFBC). Applied Thermal
      Engineering, 30, 347-353.



              Francisco dos Santos Cavalcante Junior holds a degree in physics from the State University of Ceará. He is
              currently a student at the Master Program in Applied Physics of that university. In that program he conducts
              research related to renewable energy with emphasis on biomass combustion



              José Cleiton S. Alves graduated in Mechatronic Technology (emphasis in Electrical Engineering) from the
              Federal Technological Institute of Ceará (2005), graduated in physics from State University of Ceará (2004)
              and Master of Science in applied physics from UECE, with an emphasis on Alternative Energies. Currently
              he is working on PetroleoBrasileiro S/A - PETROBRAS serving as the technical operations at the LUBNOR.
              He has experiences in the areas of Physics, Automation, Robotics, Combustion, Oil and Gas.

              Dr.Francisco Sales A. Cavalcante earned his MSc (1996) and PhD(2000) in Physic from Universidade
              Federal do Ceará. His researches are in renewable energy, atmospheric pollution and respiratory mechanics.




              Dr.Lutero Carmo de Lima graduated in Physics by the University of Santo Amaro, M.Sc. and Dr. Eng. in
              Mechanical Engineering by the Federal University of Santa Catarina and University of São Paulo,
              respectively. He is presently adjunct Professor at the State University of Ceará and basically works in
              fundamental problems of the thermal science, clean energy and instrumentation. He was awarded a
              Fulbright Fellow and inducted as Vice President of PHI BETA DELTA, Chapter Beta Theta, Honour Society
              for International Scholars, USA.

Peer Review: This article has been internationally peer-reviewed and accepted for publication
             according to the guidelines given at the journal’s website.




* Corresponding author (Francisco S. Cavalcante Junior). Tel/Fax: +55-85-31019902. E-mail
address: juniornum@gmail.com       2012 International Transaction Journal of Engineering,
Management, & Applied Sciences & Technologies.       Volume 3 No.4         ISSN 2228-9860                     465
eISSN 1906-9642. Online Available at http://TuEngr.com/V03/455-465.pdf

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International Transaction Journal of Engineering, Management, & Applied Sciences

  • 1. 2012 International Transaction Journal of Engineering, Management, & Applied Sciences & Technologies. International Transaction Journal of Engineering, Management, & Applied Sciences & Technologies http://TuEngr.com, http://go.to/Research Parameters Analysis of the Assisted Combustion of Residual Biodiesel Glycerol a* a Francisco S. Cavalcante Junior , José Cleiton S. Alves , a a Francisco Sales A. Cavalcante , and Lutero C. de Lima a Graduate Program on Applied Physics, State University of Ceará, BRAZIL ARTICLEINFO A B S T RA C T Article history: With the increased production of biodiesel, an excess of Received 26 July 2012. glycerol is being generated worldwide. One way to reduce the surplus of Received in revised form 03 September 2012. glycerol would be to use it as low calorific fuel in the own process of Accepted 12 September 2012. biodiesel production. However, being a high viscosity fuel with also Available online 14 September high ignition point, its combustion requires severe control and 2012. monitoring due to the formation of the toxic pollutants. It is common Keywords: practice mainly in developing countries to use biomass fuels in rural Biodiesel; regions and it looks that with glycerol will not be different. The present Glycerol; article had as objective the construction of a simple chamber for the LPG Combustion. assisted combustion of the biodiesel residual glycerol and the evaluation of all parameters related to the combustion itself. At a fixed mass flow of LPG different mass flows of glycerol were burnt and parameters such as O2, CO, CO₂, NOx, exhaust gases temperature, combustion efficiency and excess air were measured. 2012 International Transaction Journal of Engineering, Management, & Applied Sciences & Technologies. 1. Introduction  With the increase in world production of biodiesel, an excess of glycerol has being generated and many biodiesel producers can no longer give a suitable destination for the huge amount of produced glycerol. As consequence this brings not only reduction of price of glycerol but also the concern about impacts caused by the discharge of glycerol to the environment without adequate treatment (Fernando et al., 2007). Volumetrically, for every 10 * Corresponding author (Francisco S. Cavalcante Junior). Tel/Fax: +55-85-31019902. E-mail address: juniornum@gmail.com 2012 International Transaction Journal of Engineering, Management, & Applied Sciences & Technologies. Volume 3 No.4 ISSN 2228-9860 455 eISSN 1906-9642. Online Available at http://TuEngr.com/V03/455-465.pdf
  • 2. liters of biodiesel produced, a liter of glycerol is generated as residue. Glycerol is a co-product from the production of biodiesel and its chemical nomenclature is propane-1,2,3-triol, an organic compound belonging to the family of alcohol. It is odorless, hygroscopic and viscous. The glycerol with purity above 95% is also called glycerin and in its raw form has low commercial value because it may contain residues of methanol, sodium hydroxide, fatty acids, salts, sulfur and other contaminants (Barbosa, 2008). It is used primarily in the food, pharmaceutical and chemical industries. According to the National Petroleum Agency in 2008 Brazil has produced 1.17 billion liters of biodiesel. The production of glycerol was of about 117 million liters however in that year only 11 million liters was consumed by the Brazilian market. As highlighted before many biodiesel producers are concerned about not knowing what to do with the large amounts of glycerol produced. In the recent literature there are many articles related to different applications of glycerol. To name a few, Arechederra et al. (2007) performed experiments using glycerol as a source for a fuel cell. According to the researchers there are some peculiar characteristics that make glycerol a good alternative for this application because it is non-toxic, non-volatile, non-flammable at low temperatures, has high energy density, and is abundant due to the fact that it is a byproduct of biodiesel production. Adhikari et al. (2009) made a review of different generation methods, catalysts and operating conditions used to produce hydrogen using glycerol as a substrate. They stressed that most of the studies were focused on hydrogen production via steam reforming process and few work has been done on producing hydrogen from crude glycerol. According to Bohon et al. (2011) one possible use for the excessive surplus of glycerol in the market is to use it as a boiler fuel to produce steam and co-generate electricity and if combined with biodiesel production, this has the added advantages of optimizing energy integration, eliminating transportation costs, and displacing the need for fossil fuels. Striugas et al. (2008) made analysis of combustion of emulsions of glycerol and heavy fuel oil. They made comparison on emissions of NOx, SO2 and CO from the emulsions with the emissions of heavy fuel oil and they found better indexes of emission for the emulsions. Still, according to Striugas et al. (2008), it is difficult to atomize with conventional equipment because of its high density and viscosity, which means that it must be heated in advance. In fact, glycerol has quite a high auto-ignition temperature (370 °C) compared to other liquid fuels, so it flames up with difficulty. Another consideration highlighted by Striugas et al. is that when glycerol is heated around 280 °C, toxic acrolein is produced. They made research about the use of glycerol to 456 Francisco S. C. Junior, José C. S. Alves, Francisco S. A. Cavalcante a, and L.C. de Lima
  • 3. produce fuel emulsions containing heavy fuel oil. They observed that the burning of such emulsions leads to the decrease in the emission of sulphur dioxide by up to six-fold less than the concentration produced by burning pure heavy fuel oil. They observed too that the concentration of NOx, CO, and SO₂ in the flue gases did not exceed the permissible levels of pollutants emitted from fuel combustion plants, as specified in EU Council Directives. Patzer (2007) studied the combustion of mixture of glycerol and yellow grease in a chamber without specific adaptations and according to the author the results for the mixture presented better results than the combustion of raw glycerol. The same author stressed that it was not possible to realize a stable process of combustion due to the peculiar characteristics of raw glycerol as a fuel. Asavatesanupap and Santikunaporn (2010) presented a feasibility study on the production of solid fuel from glycerol and agricultural wastes. They mixed ground crop residues, dried durian shell and bagasse with glycerol from biodiesel in various weight ratios. They concluded that solid fuel derived from either dried durian shell or bagasse and glycerol can be used as an alternative fuel according to their energy contents even though amount of acrolein is fairly excessive. Bohon et al. (2011) developed a system where the glycerol is pressurized and injected into a combustion chamber. They reported a range of emissions measurements, including nitrogen oxides, total hydrocarbons, and particle mass for two grades of crude glycerol (methylated and demethylated) and compared these to No. 2 fuel oil and propane. They concluded that a properly designed refractory burner can provide the thermal environment to effectively combust glycerol, but that high particulate emissions due to residual catalyst are likely to be an issue for crude glycerol combustion. Differently from all authors cited above, in the present article the combustion of raw glycerol was made in a simply designed chamber in combination with LPG. In fact LPG was the main fuel in the combustion and glycerol entered as an aggregate aiming to reduce the consumption of LPG. Almost every possible parameters of combustion were evaluated. Parameters such O2, CO, CO2, NOx, excess air, combustion efficiency and exhaust gases temperature were measured. These measurements have presented an interesting aspectwhich is the possibility to use raw glycerol as an energetic aggregate to the combustion of LPG representing potentially reduction in the consumption of such important fuel. * Corresponding author (Francisco S. Cavalcante Junior). Tel/Fax: +55-85-31019902. E-mail address: juniornum@gmail.com 2012 International Transaction Journal of Engineering, Management, & Applied Sciences & Technologies. Volume 3 No.4 ISSN 2228-9860 457 eISSN 1906-9642. Online Available at http://TuEngr.com/V03/455-465.pdf
  • 4. 2. Material and Methods  Figure 1 shows a schematic diagram of chamber with accessories designed for the assisted combustion of raw glycerol. The chamber dimensions is 0.75 m height, 0.60 m width and 0.60 m depth and the experimental setup consists of (1) a raw glycerol recipient, (2) valves for the control of glycerol and LPG mass flows, (3) a stainless duct of 3.7 mm internal diameter, (4) inlet to the flue gases analyser, (5) a chimney of 2.4 m length and 6.5 cm internal diameter, (6) a commercial atmospheric LPG burner, (7) a LPG filter, and (8) a LPG tank. Figure 1: Schematic diagram of the experimental setup. The LPG burner (Jackwal® - Brazil) with the nominal gas consumption of 0.19 kg/h was permitted to work until steady-state regime was reached and the oxygen concentration in the flue gases was adjusted to 6.0%. The 6.0% of oxygen in the flue gases is an established criterion in the literature in order to quantify the emission of pollutants in combustion processes (Kuprianov et al., 2010).Raw glycerol at mass flows of 0.036, 0.072, .108 and 0.144 kg/h was fed to the preheated combustion chamber through a stainless duct as shown in Fig. 1. The glycerol feeding duct was maintained parallel and close to the head of the LPG burner in such a way that it burned inside the LPG flame. The glycerol used was produced in the biodiesel plant in the State of Ceará – Brazil by the Petrobrás Biofuels Company. Basically the biodiesel produced in such Company 20% is derived from cotton and 80% is derived from soybeans. As provided by Petrobrás the glycerol sample contains 81.8% glycerol, 9.8% water, 5.8% ash, and 2.6% organic material. 458 Francisco S. C. Junior, José C. S. Alves, Francisco S. A. Cavalcante a, and L.C. de Lima
  • 5. According to Metzger (2007) one kilogram of glycerol contains less chemical energy than kerosene and gasoline. Glycerol has an average of 16 MJ per kilogram of chemical energy and kerosene 42.8 MJ and gasoline 44.4 MJ. All combustion parameters were measured by the flue gases analyser TESTO 330-2 LL. Such analyser has cells for the measurement of oxygen, carbon monoxide and nitrogen oxides. It has also thermocouples for the measurement of the ambient and flue gases temperatures. As provided by the manufacturer of such equipment the uncertainty for the measurement of O₂ is ±0.2%. For the measurement of temperature the uncertainty is ±0.5 °C and for the measurement of the other parameters (CO₂, CO, and NOx) the uncertainty was of ±5%. 3. Results and Discussion  Figure 2 presents the oxygen concentration in the flue gases as a function of the glycerol mass flow. As stressed before, the zero mass flow of glycerol corresponds to the situation where only the LPG burner is working and the concentration of oxygen in the flue gases was fixed at 6.0%. For the glycerol mass flows of 36 to 108 g/h the oxygen concentration was in average 5.8% and for the mass flow of 144 g/h the oxygen concentration decreased to 5.3%. Figure 2: O₂ concentration in the flue gases for different glycerol mass flows Figure 3 presents the concentration of carbon monoxide as a function of the glycerol mass flow. The percentage of CO increases with the increase in the glycerol mass flow. At zero flow of glycerol and at the fixed percentage of oxygen 6.0% considered for the only combustion of * Corresponding author (Francisco S. Cavalcante Junior). Tel/Fax: +55-85-31019902. E-mail address: juniornum@gmail.com 2012 International Transaction Journal of Engineering, Management, & Applied Sciences & Technologies. Volume 3 No.4 ISSN 2228-9860 459 eISSN 1906-9642. Online Available at http://TuEngr.com/V03/455-465.pdf
  • 6. LPG the CO concentration was of 15 ppm. It increased to 178 ppm at the glycerol mass flow of 144 g/h. Gonzalez et al. (2004) considered that this behavior is due to the fact that the furnace temperature rises as the mass flow increases and this contributes to the endothermic reaction C + CO₂ ↔ 2CO. At the other hand, Kuprianov et al.(2010) consider that the CO emission exhibits strong influences of both excess air and fuel quality comprehending carbon content and moisture. In general CO decreases with the increase in the excess air. So the reason for the increase of CO as a function of the increase in the glycerol mass flow is possibly due the carbon content of the raw glycerol used since the level of moisture in all samples tested was the same. Figure 3: CO concentration in the flue gases for different glycerol mass flows. Figure 4 presents the temperature and the percentage of carbon dioxide in the flue gases for all glycerol mass flows. It is observed that the percentage of CO₂ increases simultaneously with the increases of the flue gases temperature and glycerol mass flow. This can be explained by the fact that the combustion efficiency can be put as a function of the sensitive heat and not-burnt gaseous losses of the fumes. However the sensitive heat is dependent on the flue gases CO₂ besides fumes and ambient temperature (Gonzales et al., 2004). As also it can be seen in Figure 5 the combustion efficiency kept practically constant (around 83%) at the glycerol flows tested. 460 Francisco S. C. Junior, José C. S. Alves, Francisco S. A. Cavalcante a, and L.C. de Lima
  • 7. Figure 4: CO₂ and flue gases temperature for different glycerol mass flows. Gonzalez et al. (2004) observed that fuel mass flow scarcely influences combustion process efficiency, corroborating the finding of this study as depicted in Figure 5. Interestingly, Miranda et al. (2007) didn’t reach the same conclusion when they studied combined combustion of various phase of olive wastes in a conventional combustor under varying fuel mixture and mass flows. Figure 5: Combustion efficiency against glycerol mass flow. Figure 6 presents the excess air as a function of the glycerol mass flow. For the reference condition where the only LPG combustion was maintained at 6.0% of oxygen in the flue gases the excess air was of 44.8%. With the introduction of glycerol the excess air decreased to 33.7% * Corresponding author (Francisco S. Cavalcante Junior). Tel/Fax: +55-85-31019902. E-mail address: juniornum@gmail.com 2012 International Transaction Journal of Engineering, Management, & Applied Sciences & Technologies. Volume 3 No.4 ISSN 2228-9860 461 eISSN 1906-9642. Online Available at http://TuEngr.com/V03/455-465.pdf
  • 8. at the mass flow of 144 g/h. This behavior is in some way expected since the more is the mass flow of glycerol the more the oxygen needed for completing the combustion. Figure 6: Excess air for different glycerol mass flow. In order to effectively quantify the emission of pollutants resulted from the assisted combustion of raw glycerol the O₂ was fixed at 6.0% in dry basis and the values of CO and NOx were measured for different mass flows of glycerol. As already shown in Fig. 2, for no flow of glycerol and only burning LPG CO reached 15 ppm. This value reached 81 ppm for the flow of 36 g/h and increased to 178 ppm when the glycerol mass flow was 144 g/h. The same tendency of CO emission was observed by other researchers. Miranda et al. (2007) measured CO under the same basis (O₂ 6.0%) and found value of about 2000 ppm for the combustion of olive kernel, 5000 ppm for the combustion of pulp and 2500 ppm for the combustion of residual olive pomace. Kuprianov et al.(2010) also for the same condition found values of CO at 350 ppm during the combustion of moisturized rice husk in a swirling fluidized-bed combustor. At other hand, Madhiyanon et al. (2010) found for the same condition values at the range of 50 to 550 ppm depending on the bed temperature of the combustion of rice-husk in a short combustion-chamber-chamber fluidized-bed combustor. Figure 7 presents the emission of NOx as a function of glycerol mass flows at the condition of O₂ fixed at 6.0% for the flue gases under dry basis. For the condition of only burning LPG the emitted NOx was 36 ppm. For almost all glycerol mass flows the NOx emissions were about 27 ppm. However at mass flow of 144 g/h the emission reached 29 ppm. Bohon et al. (2011) 462 Francisco S. C. Junior, José C. S. Alves, Francisco S. A. Cavalcante a, and L.C. de Lima
  • 9. found NOx emissions of 7 to 10 ppm for one of their prototype burner under the condition of 0% O₂ and of 160 to 240 ppm for other refractory-lined furnace. They considered differences in burner swirl and excess air, as well as differences in compositions between pure glycerol and actual crude glycerol wastes as the responsible. Miranda et al. (2007) found 50 to 120 ppm of NOx emission for their combined combustion of olive combustor. Their emission increased with the increase of the mass flow and flame temperature. Kuprianov et al. (2010) measured NOx at about 170 ppm and reduced it to 128 ppm when the best combustion and emission performance of the SFBC was achievable and when burning moisturized rice husk with moisture content of 2-25%, at excess air of 40-50%. Madhiyanon et al. (2010) reached almost the same range as Kuprianov et al. (2010) when they burned rice husk in SFB combustor. Figure 7: NOx emission at 6.0% O₂ for different glycerol mass flow 4. Conclusion  The LPG assisted combustion of different glycerol mass flows of raw glycerol in a simply designed chamber was realized in this study. Although glycerol is not considered a conventional fuel and presents many problems for its combustion, results in this study indicated that it is possible to burn glycerol. The emission level of CO under the condition of 6.0% O₂ in the flue gases (and in the literature established control condition for the measurements of CO and NOx emissions) for different glycerol mass flows and constant LPG mass flow was considered very high. However the emission of NOx under the same condition was quite low when compared with published experiments of biomass combustion. The pressurized spray of * Corresponding author (Francisco S. Cavalcante Junior). Tel/Fax: +55-85-31019902. E-mail address: juniornum@gmail.com 2012 International Transaction Journal of Engineering, Management, & Applied Sciences & Technologies. Volume 3 No.4 ISSN 2228-9860 463 eISSN 1906-9642. Online Available at http://TuEngr.com/V03/455-465.pdf
  • 10. glycerol, the formation of ash, particulate matters, and acrolein on the fumes are continued problems for the combustion of glycerol. In the present time the authors of this article are tackling such problems. 5. Acknowledgements  One of the authors (F.S.A. Cavalcante) thanks the Brazilian National Council for Scientific and Technological Development (CNPq) for financial support. 6. References  Fernando S., Adhikari S., Kota K.,Bandi R. (2007). Glycerol base automotive fuels from future biorefineries.Fuel, 86, 2806-9. Barbosa C.R. (2008). Evaluation of glycerol derived from biodiesel production as substrate for endotoxins production by Bacillus thuringiensis var. israelensis.Dissertation (Master of Science in Industrial Biotechnology) - Engineering School of Lorena, University of São Paulo, Lorena, São Paulo. Agência Nacional do Petróleo, Gás Natural e Biocombustíveis (ANP). Dados Estatísticos Mensais(In Portuguese). Avaialableat<http://www.anp.gov.br/?pg=56046&m=&t1=&t2=&t3=&t4=&ar=&ps= &cachebust=1312202333159> (accessed August 2011). Arechederra R.L., Treu B.L., Minteer S.D. (2007). Development of glycerol/O₂ biofuel cell.Journal of Power Sources, 173, 156-161. Adhikari S., Fernando S.D., Haryanto A. (2009). Hydrogen production from glycerol: an update. Energy Conversion and Management, 50, 2600-4. Bohon MD, Metzger BA, Linak WP, King CJ, Roberts WL. Glycerol combustion and emissions.Proceedings of the Combustion Institute, 33, 2717-24. Striugas N., Šlančiauskas A., Makarevičienė V., Gumbytė M., Janulis P. (2008). Processing of the glycerol fraction from biodiesel production plants to provide new fuels for heat generation.Energetika. 54, 5-12. Patzer R., Norris M., Doering A., Jorgenson R.,Neece C. (2007).Emissions evaluation: Combustion of crude glycerin and yellow grease in an industrial fire tube boiler. Agricultural Utilization Research Institute, available at <http://www.auri.org/research/glycerin%20report%20final.pdf> (accessed November 2010). Asavatesanupap C., Santikunaporn M.A. (2010). Feasibility study on production of solid fuel from glycerol and agricultural wastes.International Transaction Journal of Engineering, Management, & Applied Sciences & Technologies, 01, 43-51. 464 Francisco S. C. Junior, José C. S. Alves, Francisco S. A. Cavalcante a, and L.C. de Lima
  • 11. Kuprianov V.I., Kaewklum R., Sirisomboon K., Arromdee P., Chakritthakul S. (2010). Combustion and emission characteristics of a swirling fluidized-bed combustor burning moisturized rice husk. Appl. Energy. 87, 2899-2906. Metzger, B. Glycerol Combustion, Master Thesis, North Carolina State University, Raleigh, North Carolina, 2007. Gonzalez J.F., Gonzalez-Garcia C.M., Ramiro A., Gonzalez J.,Sabio E., Ganan J., Rodriguez M.A. (2004). Combustion optimisation of biomass residue pellets for domestic heating with a mural boiler. Biomass and Bioenergy, 27, 145-154. Miranda M.T., Cabanillas A., Rojas S., Montero I., Ruiz A. Combined combustion of various phases of olive wastes in a conventional combustor. Fuel, 86, 367-372. Madhiyanon T, Sathitruangsak P, Soponronnarit S. Combustion characteristics of rice-husk in a short-combustion-chamber fluidized-bed combustor (SFBC). Applied Thermal Engineering, 30, 347-353. Francisco dos Santos Cavalcante Junior holds a degree in physics from the State University of Ceará. He is currently a student at the Master Program in Applied Physics of that university. In that program he conducts research related to renewable energy with emphasis on biomass combustion José Cleiton S. Alves graduated in Mechatronic Technology (emphasis in Electrical Engineering) from the Federal Technological Institute of Ceará (2005), graduated in physics from State University of Ceará (2004) and Master of Science in applied physics from UECE, with an emphasis on Alternative Energies. Currently he is working on PetroleoBrasileiro S/A - PETROBRAS serving as the technical operations at the LUBNOR. He has experiences in the areas of Physics, Automation, Robotics, Combustion, Oil and Gas. Dr.Francisco Sales A. Cavalcante earned his MSc (1996) and PhD(2000) in Physic from Universidade Federal do Ceará. His researches are in renewable energy, atmospheric pollution and respiratory mechanics. Dr.Lutero Carmo de Lima graduated in Physics by the University of Santo Amaro, M.Sc. and Dr. Eng. in Mechanical Engineering by the Federal University of Santa Catarina and University of São Paulo, respectively. He is presently adjunct Professor at the State University of Ceará and basically works in fundamental problems of the thermal science, clean energy and instrumentation. He was awarded a Fulbright Fellow and inducted as Vice President of PHI BETA DELTA, Chapter Beta Theta, Honour Society for International Scholars, USA. Peer Review: This article has been internationally peer-reviewed and accepted for publication according to the guidelines given at the journal’s website. * Corresponding author (Francisco S. Cavalcante Junior). Tel/Fax: +55-85-31019902. E-mail address: juniornum@gmail.com 2012 International Transaction Journal of Engineering, Management, & Applied Sciences & Technologies. Volume 3 No.4 ISSN 2228-9860 465 eISSN 1906-9642. Online Available at http://TuEngr.com/V03/455-465.pdf