Degradation of phorbol esters Degradation of phorbol esters Degradation of phorbol esters with an atmospheric pressure with an atmospheric pressure with an atmospheric pressure plasma jet plasma jet plasma jet ISPlasma 2013 (2013/2/1、Nagoya) Osaka Prefecture University H.Matsuura, S.Kongmany M.Furuta, K.Imamura,Y.Maeda and S.Okuda
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(201 3/2/1 Nagoya) - 大阪府立大学matsu/data/isplasma5/...3 Phorbol Esters Phorbol Esters Introduction Introduction Introduction Introduction J. Curcas J. Curcas seed seed kernel
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Degradation of phorbol esters Degradation of phorbol esters Degradation of phorbol esters
Degradation of phorbol esters
with an atmospheric pressure with an atmospheric pressure with an atmospheric pressure
with an atmospheric pressure
plasma jetplasma jetplasma jet
plasma jet
ISPlasma 2013(2013/2/1、Nagoya)
Osaka Prefecture UniversityH.Matsuura, S.Kongmany
M.Furuta, K.Imamura,Y.Maeda and S.Okuda
Jatropha curcas (J. curcas) currently is the best candidate as the raw material for producing biodiesel since it contains lots of oil of approximately 60%.
But the Jatropha oil produced contains the toxic components of phorbolesters that act a cancer promoter. Nowadays, the solution for solving this problems by various physical and chemical means is investigating all over the world.
Sunlight(UV?)Ultrasonic waveGamma-ray
Atmospheric pressure plasma is also found to provide reactive free radicals to convert the phorbol ester into original phorbol. We now start measurement radical concentration in the solution to study the mechanism of degradation and to compare the efficiency of degradation methods.
Background
3
Phorbol EstersPhorbol EstersPhorbol Esters
Phorbol Esters
IntroductionIntroductionIntroduction
Introduction
IntroductionIntroductionIntroduction
Introduction
J. Curcas J. Curcas J. Curcas
J. Curcas
seed seed seed
seed
kernelkernelkernel
kernel
Mechanical Mechanical Mechanical
Mechanical
extraction of extraction of extraction of
extraction of
oiloiloil
oil
Biodiesel Biodiesel Biodiesel
Biodiesel
productionproductionproduction
production
Livestock Livestock Livestock
Livestock
feedingfeedingfeeding
feeding
Crude J. curcas OilCrude J. curcas OilCrude J. curcas Oil
Crude J. curcas Oil
J. Curcas seed cakeJ. Curcas seed cakeJ. Curcas seed cake
• One of the exploitation of renewable sources of energy:One of the exploitation of renewable sources of energy:One of the exploitation of renewable sources of energy:
One of the exploitation of renewable sources of energy:
• The production of biodiesel via esterification or transesterification:The production of biodiesel via esterification or transesterification:The production of biodiesel via esterification or transesterification:
The production of biodiesel via esterification or transesterification:
• Edible vegetable oils and animal fats, etc.Edible vegetable oils and animal fats, etc.Edible vegetable oils and animal fats, etc.
• In 2015, 12.8 Mt of J. curcas oil will be produced (GEXST, 2008).In 2015, 12.8 Mt of J. curcas oil will be produced (GEXST, 2008).In 2015, 12.8 Mt of J. curcas oil will be produced (GEXST, 2008).
In 2015, 12.8 Mt of J. curcas oil will be produced (GEXST, 2008).
70-75% PEs70-75% PEs70-75% PEs
70-75% PEs
20-25% PEs20-25% PEs20-25% PEs
20-25% PEs
PlasmPlasmaa Degradation of phorbol estersDegradation of phorbol esters• Mixed 4 standard phorbol ester in methanol were exposed to plasma channel at
constant He flow and applied voltage. The plasma ionizing time was optimized.
Radiation Research CenterRadiation Research CenterRadiation Research Center
Radiation Research Center
Fig. 5 Fig. 5 Fig. 5
Fig. 5
Atmospheric pressure plasma jet for degradation of mixed 4 phorbol esters solution.
Radiation Research CenterRadiation Research CenterRadiation Research Center
Radiation Research Center
aaa
a
bbb
b
ccc
c
Fig. 11 Fig. 11 Fig. 11
Fig. 11
Degradation profile of mixed 4 phorbol esters before and after plasma ionization: (a) &(b) the comparison of HPLC/UV chromatogram and (c) concentration and degradation of phorbol esters.
HPLC/UV chromatograms of aqueous solution of: (a) HPLC/UV chromatograms of aqueous solution of: (a) HPLC/UV chromatograms of aqueous solution of: (a)
HPLC/UV chromatograms of aqueous solution of: (a)
TPA and (b) mixed jatropha phorbol esters (4 peaks each TPA and (b) mixed jatropha phorbol esters (4 peaks each TPA and (b) mixed jatropha phorbol esters (4 peaks each
TPA and (b) mixed jatropha phorbol esters (4 peaks each
peak corresponding to each type of jatropha factor) peak corresponding to each type of jatropha factor) peak corresponding to each type of jatropha factor)
peak corresponding to each type of jatropha factor)
before and after plasma irradiation for 15 min.before and after plasma irradiation for 15 min.before and after plasma irradiation for 15 min.
National University of Laos, Faculty of Science, Department of ChemistryNational University of Laos, Faculty of Science, Department of ChemistryNational University of Laos, Faculty of Science, Department of Chemistry
National University of Laos, Faculty of Science, Department of Chemistry
• TheTheThe
The
phorbol ester phorbol ester phorbol ester
phorbol ester
may be converted into may be converted into may be converted into
may be converted into
original phorbol original phorbol original phorbol
original phorbol
since it has since it has since it has
since it has
ever taken place during the transesterification process of J. curcas oil ever taken place during the transesterification process of J. curcas oil ever taken place during the transesterification process of J. curcas oil
ever taken place during the transesterification process of J. curcas oil
• By using UV Chromatogram, degradation of Phorbol ester with atmospheric plasma and is confirmed.
• Concentration of hydroxyl radicals (OH) is estimated with KI-colorimetric method, of which result does not contradict with Prof. Kanazawa's work with the similar plasma device and different measurement method.
Future works• Test using PE with much simpler structure
to study degradation mechanism
• Control plasma parameters and study the relation between OH concentration and degradation effect
• Direct confirm of detoxification with biological manners, not merely disappear of Phorbol Ester
Appendix
Why Why Why
Why
is J. curcas used for biodiesel production if it contains PEs?is J. curcas used for biodiesel production if it contains PEs?is J. curcas used for biodiesel production if it contains PEs?
is J. curcas used for biodiesel production if it contains PEs?
Oil yield: Jatropha vs other seed crops.Oil yield: Jatropha vs other seed crops.Oil yield: Jatropha vs other seed crops.
Malaysia 0.23 W. A. Ahmed et al. , Phorbol Ester as Toxic Constituents of Tropical Jatropha Curcas Seed Oil, European Journal of
Scientific Research ISSN 1450-216X Vol.31 No.3 (2009), pp.429-436
Indonesia 1.58
India 0.58
Vietnam
Son La 0.62
Research Report for NEDO’s Northern part 0.19
Binh Thuan 0.27
Thailand
Chiang Mai 0.01Donlaporn Saetae and Worapot Suntornsuk, Variantion of Phorbol Ester Contents in Jatropha curcas from Different Provinces in Thailand and the Application of its Seed Cake
for Starter Broiler Diets, American-Eurasian J. Agric. & Environ. Sci., 8 (5): 497-501, 2010
Phrae 0.03
Phitsanulok 0.02
Satun 0.03
Oil Refining: Oil Refining: Oil Refining:
Oil Refining:
Role and Reduction/degradation of PEsRole and Reduction/degradation of PEsRole and Reduction/degradation of PEs
Role and Reduction/degradation of PEs
Sources: Sources: Sources:
Sources:
H. Makkar et al., Removal and Degradation of Phorbol Esters during Pre-treatment and Transesterification of H. Makkar et al., Removal and Degradation of Phorbol Esters during Pre-treatment and Transesterification of H. Makkar et al., Removal and Degradation of Phorbol Esters during Pre-treatment and Transesterification of
H. Makkar et al., Removal and Degradation of Phorbol Esters during Pre-treatment and Transesterification of
Jatropha curcas Oil, J Am Oil Chem Soc (2009) 86:173Jatropha curcas Oil, J Am Oil Chem Soc (2009) 86:173Jatropha curcas Oil, J Am Oil Chem Soc (2009) 86:173
Jatropha curcas Oil, J Am Oil Chem Soc (2009) 86:173
–––
–
181181181
181
Oil RefiningOil RefiningOil Refining
Oil Refining
DegummingDegummingDegumming
Degumming
DeacidificationDeacidificationDeacidification
Deacidification
BleachingBleachingBleaching
Bleaching
DeodorizationDeodorizationDeodorization
Deodorization
Refined Refined Refined
Refined
OilOilOil
Oil
Degummed oilDegummed oilDegummed oil
Degummed oil
Acid gums Acid gums Acid gums
Acid gums
and and and
and
waste waterwaste waterwaste water
waste water
Distillation at 260oC under vacuum to remove undesirable volatile and odoriferous materials.
Interacting with bleaching agents to remove undesirable coloured impurities, remaining trace phospholipids, soap, metals and oxidation products.
Reacting with NaOH to neutralize remaining H3PO4 and/or Free fatty acids.
Interacting with H3PO4 to remove phosphatides in the form of gum.
there any risks of J. curcas PEs to environment?there any risks of J. curcas PEs to environment?there any risks of J. curcas PEs to environment?
there any risks of J. curcas PEs to environment?
Sources: Sources: Sources:
Sources:
H. Makkar et al., Removal and Degradation of Phorbol Esters during Pre-treatment and Transesterification of H. Makkar et al., Removal and Degradation of Phorbol Esters during Pre-treatment and Transesterification of H. Makkar et al., Removal and Degradation of Phorbol Esters during Pre-treatment and Transesterification of
H. Makkar et al., Removal and Degradation of Phorbol Esters during Pre-treatment and Transesterification of
Jatropha curcas Oil, J Am Oil Chem Soc (2009) 86:173Jatropha curcas Oil, J Am Oil Chem Soc (2009) 86:173Jatropha curcas Oil, J Am Oil Chem Soc (2009) 86:173
Jatropha curcas Oil, J Am Oil Chem Soc (2009) 86:173
National University of Laos, Faculty of Science, Department of ChemistryNational University of Laos, Faculty of Science, Department of ChemistryNational University of Laos, Faculty of Science, Department of Chemistry
National University of Laos, Faculty of Science, Department of Chemistry
• The PEs’ structure is dependent on the tetracyclic diterpene carbon skeleton (Tigliane).• PEs are hydrophobic, oil soluble and head stable when present in oil or seed cake.
During Transesterification of J. curcas oil containing PEs, PEs are During Transesterification of J. curcas oil containing PEs, PEs are During Transesterification of J. curcas oil containing PEs, PEs are
During Transesterification of J. curcas oil containing PEs, PEs are
converted into Phorbol dissolving into glycerin phase.converted into Phorbol dissolving into glycerin phase.converted into Phorbol dissolving into glycerin phase.
converted into Phorbol dissolving into glycerin phase.
PEs containing in J. curcas seed cake can possibly degraded by PEs containing in J. curcas seed cake can possibly degraded by PEs containing in J. curcas seed cake can possibly degraded by
PEs containing in J. curcas seed cake can possibly degraded by
several means proposed by some authors. Then it can be used for several means proposed by some authors. Then it can be used for several means proposed by some authors. Then it can be used for
several means proposed by some authors. Then it can be used for
livestock feed.livestock feed.livestock feed.
livestock feed.
Livestock Livestock Livestock
Livestock
feedingfeedingfeeding
feeding
J. Curcas seed cakeJ. Curcas seed cakeJ. Curcas seed cake
J. Curcas seed cake
20-25% PEs20-25% PEs20-25% PEs
20-25% PEs
Degradation by some approachDegradation by some approachDegradation by some approach
Degradation by some approach
Treatment methodTreatment methodTreatment method
Treatment method
ConditionConditionCondition
Condition
(%) Removal or(%) Removal or(%) Removal or
(%) Removal or
DegradationDegradationDegradation
Degradation
ReferencesReferencesReferences
References
stripping/deodorization at 260oC, 3 mbar and 1% steam injection
~ 100 Makkar et al. (2009)
alkali and heat treatment [1:1 (w/v) alkali, autoclaving at 121oC].
89 Rakshit et al. (2008)
Extraction with methanol and treatment with 0.07% NaHCO3
97 Martınez-Herrera et al. (2006).
Washing with methanol Autoclave heating at 121oC 95 Aregheore et al. (2003)
Solid State Fermentation (SSF) Pseudomonas aeruginosa PseA strain, 9 days
~ 100 Chetna Joshi et al. (2011)
Air bubbling autoclaving before and after treatment.
78.53 Sh. A. El Rafei et al (2011)
NaHCO3 and ozonation Ozone does: 50 mg/L, 3 min. 75.26 Sh. A. El Rafei et al (2011)
Γ-irradiation γ-ray dose of 50 kGy for 30 min. 71.35 Sh. A. El Rafei et al (2011)
What What What
What
are the new methods proposed to do?are the new methods proposed to do?are the new methods proposed to do?
are the new methods proposed to do?
According to literature reviewAccording to literature reviewAccording to literature review
According to literature review
, the degradations of PEs the degradations of PEs the degradations of PEs
the degradations of PEs
are based on the conventional and aaa
a
dvance ooo
o
xidative processesprocessesprocesses
processes
(AOP) such as
• combination with chemical and heat treatmentcombination with chemical and heat treatmentcombination with chemical and heat treatment
combination with chemical and heat treatment
, , ,
,
• biological oxidation using microbesbiological oxidation using microbesbiological oxidation using microbes
biological oxidation using microbes
, , ,
,
• the combination of Aeration and heat treatmentthe combination of Aeration and heat treatmentthe combination of Aeration and heat treatment
the combination of Aeration and heat treatment
, , ,
,
• the combination of chemical and Ozonation the combination of chemical and Ozonation the combination of chemical and Ozonation
the combination of chemical and Ozonation
or or or
or
-irradiation-irradiation-irradiation
-irradiation
...
.
New methods are based on AOPNew methods are based on AOPNew methods are based on AOP
-Radiolytic degradation of -Radiolytic degradation of -Radiolytic degradation of
-Radiolytic degradation of
PEs.PEs.PEs.
PEs.
• The first two methods have not been studies by any author on the degradation of Jatropha PEs.• Even though -irradiation method has been used for degradation of PEs in the J. curcas seed cake, there is
not any work on the degradation of PEs in liquid media such as in oil or other solvents as well as in water.
L. WojnL. WojnL. Wojn
L. Wojn
ááá
á
rovits, E. Takrovits, E. Takrovits, E. Tak
rovits, E. Tak
ááá
á
cs, Irradiation treatment of azo dye containing wastewater: An overview,Radiation Physics and Chemistry cs, Irradiation treatment of azo dye containing wastewater: An overview,Radiation Physics and Chemistry cs, Irradiation treatment of azo dye containing wastewater: An overview,Radiation Physics and Chemistry
cs, Irradiation treatment of azo dye containing wastewater: An overview,Radiation Physics and Chemistry
cs, Irradiation treatment of azo dye containing wastewater: An overview,Radiation Physics and Chemistry cs, Irradiation treatment of azo dye containing wastewater: An overview,Radiation Physics and Chemistry cs, Irradiation treatment of azo dye containing wastewater: An overview,Radiation Physics and Chemistry
cs, Irradiation treatment of azo dye containing wastewater: An overview,Radiation Physics and Chemistry
77 (2008) 22577 (2008) 22577 (2008) 225
77 (2008) 225
–––
–
244244244
244
Reaction Reaction Reaction
Reaction
Effect ofEffect ofEffect of
Effect of
Saturation Saturation Saturation
Saturation
AtmosphereAtmosphereAtmosphere
Atmosphere
pH pH pH
pH
RangeRangeRange
Range
AdditivesAdditivesAdditives
Additives
Related reactionsRelated reactionsRelated reactions
1. 121oC, 30 min → 4 times washing with MeOH. 95 E. M. Aregheore et al., Detoxification of a toxic variety of Jatropha curcas using heat and chemical treatments, and preliminary nutritional evaluation with rats, S. Pac. J. Nat. Sci., 2003, 21, 50-56
2. 4% NaOH + 10% NaOCl → 121oC, 30 min. 93
3. 3.5% NaOH → 121oC, 30 min. 90
4. 0.07% NaHCO3 → 121oC, 25min. 75 J. Martínez-Herrera et al., Chemical composition, toxic/ antimetabolic constituents, and effects of different treatments on their levels, in four provenances of Jatropha curcas L. from Mexico, Food Chemistry 96 (2006) 80–89.
5. 0.07% NaHCO3 → -irradiation, 10 kGy 18
6. Extraction with EtOH, room temperature, 2h. 96
7. 2% NaOH/Ca(OH)2 → 121oC, 30 min. → water dispersion, 1h. 88-90
K.D. Rakshit et al., Toxicity studies of detoxified Jatropha meal (Jatropha curcas) in rats ,Food and Chemical Toxicology 46 (2008) 3621–3625.
8. Enzymatic oxidation in soil, 21 days. 100Rakshit K. D. et al., Biodegradation of Jatropha curcas phorbol esters in soil, J Sci Food Agric 2010; 90: 2090–2097
C. Joshi et al., Degradation of phorbol esters by Pseudomonas aeruginosa PseA during solid-state fermentation of deoiled Jatropha curcas seed cake, Bioresource Technology 102 (2011) 4815–4819.
11. 0.2 N NaHCO3 → Ozone dose 50 mg/L, 2-3 min. 75.26Sh. A. El Rafei et al., Ozone for Phorbol Esters Removal from Egyptian Jatropha Oil Seed Cake, Adv. Appl. Sci. Res., 2011, 2 (4):221-232
12. 121oC, 30 min → Aeration, 3 min. → 121oC, 25 min. 78.53
there any published methods of degrading J. curcas PEs?there any published methods of degrading J. curcas PEs?there any published methods of degrading J. curcas PEs?
there any published methods of degrading J. curcas PEs?
National University of Laos, Faculty of Science, Department of ChemistryNational University of Laos, Faculty of Science, Department of ChemistryNational University of Laos, Faculty of Science, Department of Chemistry
National University of Laos, Faculty of Science, Department of Chemistry
• produces strong cavitation in aqueous solution:• shock wave. • reactive free radicals (e.g., •OH, HO2•, and O•) by violent collapse of the cavitation bubble.• formation of H2O2.
• in aqueous solution, it generates: • hydrated electrons, hydrogen atoms, and • hydroxyl radicals as initial radical species.• hydrogen and hydrogen peroxide (H2O2) are
formed by their recombination reactions.
The decomposition of toxic chemicals should be contributed by these effects.
Study on Degradation of Phorbol estersStudy on Degradation of Phorbol estersStudy on Degradation of Phorbol esters
Study on Degradation of Phorbol esters
200 kHz Sonicator 60Co as γ-ray source
At different powers, amplitudes, times At different doses, times
HPLC/UV-Vis analysis of phorbol ester concentration before and after irradiation
HPLC/UV-Vis analysis of phorbol ester concentration before and after irradiation
LC-MS analysis for confirmation of compounds LC-MS analysis for confirmation of compounds
Colorimetric analysis of H2O2 formation Colorimetric analysis of H2O2 formation
National University of Laos, Faculty of Science, Department of ChemistryNational University of Laos, Faculty of Science, Department of ChemistryNational University of Laos, Faculty of Science, Department of Chemistry
National University of Laos, Faculty of Science, Department of Chemistry
28
The similar bonding structure shows their similarity in The similar bonding structure shows their similarity in The similar bonding structure shows their similarity in
The similar bonding structure shows their similarity in
reactionreactionreaction
reaction
OC
CH2OH
H
OH
H3C
O
H
OH
H3C
CH3CH3
H
CCH3
H3C(H2C)11H2CC
O
O
OCH2
CH
H2C OCR3
O
R1OCO
R2OCO
(TPA or PMA)(TPA or PMA)(TPA or PMA)
(TPA or PMA)
(Triglycerides)(Triglycerides)(Triglycerides)
(Triglycerides)
National University of Laos, Faculty of Science, Department of ChemistryNational University of Laos, Faculty of Science, Department of ChemistryNational University of Laos, Faculty of Science, Department of Chemistry
National University of Laos, Faculty of Science, Department of Chemistry
29
Simplification of Phorbol Ester StructureSimplification of Phorbol Ester StructureSimplification of Phorbol Ester Structure
Simplification of Phorbol Ester Structure
OC
CH2OHH
OH
H3CO
H
OH
H3C
CH3CH3
H
CCH3
H3C(H2C)11H2CC
O
O
O
RRR
R
111
1
RRR
R
222
2
OC
CH2OHH
OH
H3CO
H
OH
H3C
CH3CH3
H
C
R1
O
O
O
R2
Extraction of J. curcas phorbol esterExtraction of J. curcas phorbol ester• 10 g of Jatropha oil was
extracted in triplicates each with 10 mL of methanol to give 3 fractional extracts.
Radiation Research CenterRadiation Research CenterRadiation Research Center
Radiation Research Center
• 2 mL of each fraction was kept for analyzing fractional extraction profile.
• The rest of each fraction was combined.
Fig. 1 Fig. 1 Fig. 1
Fig. 1
illustration of the procedure on the extraction of phorbol esters from Jatropha oil.
FractionExtraction
(%)Conc. (ppm)
1st 57 1994.962nd 29 999.903rd 14 478.48
Fig. 6 Fig. 6 Fig. 6
Fig. 6
HPLC/UV chromatogram at 280 nm of each methanolic fractions containing phorbol esters obtained from extraction of Jatropha oil.
• Only one extraction is not enough to get J. curcas phorbol esters from the J. curcas oil.
• There were 2 groups of peaks appear at the retention time: the 1st group (unknown) was between 5.5 and 7 min; and the 2nd group (Jatropha phorbol esters) between 8.5 and 9.5 min.
Radiation Research CenterRadiation Research CenterRadiation Research Center
Radiation Research Center
Transesterification of J. curcas phorbol esterTransesterification of J. curcas phorbol ester• 2 mL of methanolic fraction containing J. curcas PEs was added onto a graduated
tube.• 0.4 mL of 10%(w/w) KOH in methanol was further added the methanolic sample in
the tube.• The mixture was gently shaken for 1 min to get homogeneous mixture. Then it was
kept in a dark place for 14 hours to complete reaction.• After completing reaction, the mixture was neutralized with 85%
H3PO4 to the pH ~ 7.
• The light-yellowish solution was transferred onto a vial for
analysis. • The light-yellowish solution was
filtered with filter-unit before
analysis by HPLC/PDA.
• After analysis, white precipitate
was found at the bottom of the vial.
Radiation Research CenterRadiation Research CenterRadiation Research Center
HPLC/UV chromatogram at 280nm of methanolic fraction before and after transesterification.
• Before transesterification the Jatropha phorbol ester appears at retention time between 8-10 min.
• After transesterification the peaks of Jatropha phorbol esters disappear due to conversion into FAME.
• The concentration of J. curcas PEs was 3.47 0.07 mg-PEs/g-Oil.
Radiation Research CenterRadiation Research CenterRadiation Research Center
Radiation Research Center
National University of Laos, Faculty of Science, Department of ChemistryNational University of Laos, Faculty of Science, Department of ChemistryNational University of Laos, Faculty of Science, Department of Chemistry
National University of Laos, Faculty of Science, Department of Chemistry
36
KOH + CH3OH CH3O- + KH+
OC
CH2OHH
OH
H3CO
H
OH
H3C
CH3CH3
H
C
R1
O
O
O
R2
CH3O-
CH3O-
OC
CH2OHH
OH
H3CO
H
OH
H3C
CH3CH3
H
C
R1
O-
O-
O
R2
CH3O
CH3O
OC
CH2OHH
OH
H3CO
H
OH
H3C
CH3CH3
H
C
R1
O-
O-
O
R2
CH3O
CH3O
-O
C
CH2OHH
OH
H3CO
H
OH
H3C
CH3CH3
H
C
R1
O
O
-O
R2
CH3O
CH3O
-O
CH2OHH
OH
H3CO
H
OH
H3C
CH3CH3
H
-O
KH+
KH+
HO
CH2OHH
OH
H3CO
H
OH
H3C
CH3CH3
H
HO
K*
K*+
Proposed Mechanism on the conversion of phorbol ester to phorbol Proposed Mechanism on the conversion of phorbol ester to phorbol Proposed Mechanism on the conversion of phorbol ester to phorbol
Proposed Mechanism on the conversion of phorbol ester to phorbol
during transesterification of J. oil in Biodiesel productionduring transesterification of J. oil in Biodiesel productionduring transesterification of J. oil in Biodiesel production
during transesterification of J. oil in Biodiesel production
Sonolytic Degradation of Jatropha PEsSonolytic Degradation of Jatropha PEsSonolytic Degradation of Jatropha PEs
Sonolytic Degradation of Jatropha PEs
Sonolysis system for chemical degradation study: (a) front Sonolysis system for chemical degradation study: (a) front Sonolysis system for chemical degradation study: (a) front
Sonolysis system for chemical degradation study: (a) front
side; (b) top side; (c) Model and max frequency; (d) side; (b) top side; (c) Model and max frequency; (d) side; (b) top side; (c) Model and max frequency; (d)
side; (b) top side; (c) Model and max frequency; (d)
Temperature control.Temperature control.Temperature control.
Temperature control.
Scope of ResultsScope of ResultsScope of Results
Scope of Results
•Degradation at Xn mg/L and kinetic data
(ln(C0/C).
•UV adsorption spectra before and after
degradation
•Degradation vs. power density.
•Effect of pH, temperature, additives.
•Ratio of H2O2 to PEs on degradation.
•etc.
(a)(a)(a)
(a)
(b)(b)(b)
(b)
(d)(d)(d)
(d)
(c)(c)(c)
(c)
Radiolytic Degradation of Jatropha PEsRadiolytic Degradation of Jatropha PEsRadiolytic Degradation of Jatropha PEs
Radiolytic Degradation of Jatropha PEs
Radiolytic Radiolytic Radiolytic
Radiolytic
Sampling racksSampling racksSampling racks
Sampling racks
A water-pool A water-pool A water-pool
A water-pool
606060
60
Co Co Co
Co
-ray irradiation facilities at -ray irradiation facilities at -ray irradiation facilities at
-ray irradiation facilities at
the Radiation Research Center, Osaka the Radiation Research Center, Osaka the Radiation Research Center, Osaka
degradation G-value and constant.•UV absorption: UV absorption: UV absorption:
UV absorption:
degradation spectra on UV adsorption•Effect of additives and saturation atmosphere vs. Effect of additives and saturation atmosphere vs. Effect of additives and saturation atmosphere vs.
Effect of additives and saturation atmosphere vs.
degradationdegradationdegradation
degradation
•etc.etc.etc.
etc.
Radiation Research CenterRadiation Research CenterRadiation Research Center
Radiation Research Center
Fig. 9 Fig. 9 Fig. 9
Fig. 9
HPLC/UV chromatogram of TPA’s 30ppm (a-b) and 50ppm (c-d) at r-ray absorption dose of 0, 10 and 20kGy, respectively.
(((
(
a)a)a)
a)
(((
(
b)b)b)
b)
(((
(
c)c)c)
c)
(((
(
d)d)d)
d)
• After exposure to -irradiation, the TPA was degraded.
• From HPLC/UV chromatogram at 220nm around 50% TPA was degraded at 10 kGy. At 20kGy, TPA degradation was greater than 90% .
• In contrast, 56% TPA was observed at HPLC/UV at 280nm when the TPA was irradiated at 10 kGy and complete degradation was observed at 20 kGy -irradiation.
-Radiolytic Degradation of TPA-Radiolytic Degradation of TPA• 30 and 50 ppm-TPA solutions was prepared by using 1000ppm TPA standard
solution dissolved in methanol.• Vials each separately containing methanol, 30-and-50ppm TPA solution was
divided into two parts for 10 and 20 kGy, respectively.
• The vials were put onto the stainless steel sample holder and exposed to -ray at absorbed dose of 10 and 20kGy, respectively.
• The vial’s color was changed to brown after r-ray exposure.
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Fig. 4 Fig. 4 Fig. 4
Fig. 4
-irradiation of TPA solution at irradiation rate of ~ 10 kGy/h.
Results on Degradation of Jatropha PEsResults on Degradation of Jatropha PEsResults on Degradation of Jatropha PEs