AU2021106404A4 - A frequently transesterification process of Jatropha curcus oil in the presence of a green solvent - Google Patents
A frequently transesterification process of Jatropha curcus oil in the presence of a green solvent Download PDFInfo
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- 241000221089 Jatropha Species 0.000 title claims abstract description 40
- 238000005809 transesterification reaction Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000002904 solvent Substances 0.000 title claims abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 75
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000003225 biodiesel Substances 0.000 claims abstract description 31
- 238000010586 diagram Methods 0.000 claims abstract description 4
- 230000000694 effects Effects 0.000 claims description 13
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 12
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 11
- 150000004702 methyl esters Chemical class 0.000 claims description 10
- 238000006140 methanolysis reaction Methods 0.000 claims description 7
- 150000003626 triacylglycerols Chemical class 0.000 claims description 6
- 238000011088 calibration curve Methods 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 238000005457 optimization Methods 0.000 claims description 2
- 238000000825 ultraviolet detection Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000004007 reversed phase HPLC Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 60
- 235000019198 oils Nutrition 0.000 description 60
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 19
- 239000002253 acid Substances 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 8
- 235000015112 vegetable and seed oil Nutrition 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 235000011187 glycerol Nutrition 0.000 description 7
- 239000008158 vegetable oil Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000007655 standard test method Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000003209 petroleum derivative Substances 0.000 description 3
- 238000013379 physicochemical characterization Methods 0.000 description 3
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000020551 Helianthus annuus Species 0.000 description 1
- 235000003222 Helianthus annuus Nutrition 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229940049918 linoleate Drugs 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 1
- 229940073769 methyl oleate Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000000700 radioactive tracer Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000013207 serial dilution Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
- C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2270/00—Specifically adapted fuels
- C10L2270/02—Specifically adapted fuels for internal combustion engines
- C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Fats And Perfumes (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
A FREQUENTLY TRANSESTERIFICATION PROCESS OF JATROPHA CURCUS OIL
IN THE PRESENCE OF A GREEN SOLVENT
5 A quality improver and environmental friendly system for fast transesterification of Jatropha
curcus oil was developed for the production of biodiesel using a continuous coil flow reactor at
70°C in the presence of a green solvent with potassium hydroxide as a catalyst. When the oil to
methanol molar ratio was 1:5, catalyst concentration 0.75 wt% of oil and flow rate 250 m/min,
transesterification was completed within 1.62 minute. The purity and conversion of biodiesel was
.0 99.040.05% analyzed by the reverse phase HPLC method.
14
Circulating water bath
70°C
Reactor R2, at 70' eco 3 t7°
(5mmn 1.D. x 5m) (5mmit 1.D. x 5m)
Reactor R4, at 70°C
(5mmlt I.D. x 5m)
Separating funnel Seprating funnel Condenser
S1 S3at 15°C
Reactor RI, at 70°C Sepratmg funnel
(5mm 1.D1 x 5m) S2
Peri taltic Per tactic Per .taltic
pun s P3 pun s P2 pun ps P1
ResevoirC Resevoir B Resevoir A
Fig.1. Schematic diagram of continuous tranaesterification of Jatropha curcus oil using coil flow
reactor.
15
Description
Circulating water bath
70°C Reactor R2, at 70' eco 3 t7° (5mmit 1.D. x 5m) Reactor R4, at 70°C (5mmn 1.D. x 5m) (5mmlt I.D. x 5m)
Separating funnel Seprating funnel Condenser S1 S3at 15°C Reactor RI, at 70°C Sepratmg funnel (5mm 1.D1 x 5m) S2 Peri taltic Per tactic Per .taltic pun s P3 pun s P2 pun ps P1
ResevoirC Resevoir B Resevoir A
Fig.1. Schematic diagram of continuous tranaesterification of Jatropha curcus oil using coil flow reactor.
A frequently transesterification process of Jatropha curcus oil in the presence of a green solvent
This invention relates to A frequently transesterification process of Jatropha curcus oil in the
presence of a green solvent.
The reduction of greenhouse gas emission has become an important and crucial step in fulfilling
the requirements mandated under the Kyoto protocol. Depletion of the world petroleum reserves
and increasing environmental concerns have stimulated the search for renewable fuels (Shay.,
.0 1993). Among the various types of alternative fuels produced from renewable resources, biodiesel,
which is derived from the oils and fats of plants and animals, has attracted considerable attention
over recent decades as a renewable, biodegradable, eco-friendly and non-toxic fuel. Other
advantage of the biodiesel is its good lubrication property that extends the engine life, its high flash
point and acceptable cold filter plugging point (CFPP) makes it very attractive as an alternative
.5 fuel, is currently becoming a fast-growing market product (Ramadhas et al., 2005; Wang et al.,
2006; Mittelbach, 1996; Mittelbach and Enzelsberger, 1999; Park et al., 2008a). Low viscosity of
fatty acid methyl esters (FAMEs) are significantly lower than the oils (Clark et al., 1984), thereby
reducing droplet size upon injection into the cylinder and facilitating combustion. Cetane indices
and gross heat of combustion per unit weight (Kanit., 1991; Saho et al., 2007) of fatty acid methyl
esters are slightly higher than oils. FAMEs have lesser tendency to polymerize three dimensionally
than the oils.
Different methods of synthesizing biodiesel have been proposed. The most common way
is the catalytic transesterification reaction of vegetable oils with a short chain alcohol, usually methanol, also known as methanolysis; this reaction is well studied and established for soybean, sunflower, Jatropha curcus and rapeseed oil, using acid or alkali as catalyst (Funguri et al., 1999).
John and Marvin 1954 have reported that transesterification proceeds rapidly in the presence of
alkaline catalyst and that reaction are about 4000 times faster than those catalyzed by the same
amount of acidic catalyst. Heterogeneous catalytic transesterification reaction requires drastic
condition and longer reaction time periods (Young et al., 2010; Kumar et al.,2010). Continuous
transesterification also has been reported (Kumar et al., 2010). In this paper, we reported a rapid
frequently transesterification in the presence of a mutual green solvent (Jatropha curcus biodiesel)
for methanol and Jatropha curcus oil. Biodiesel is a good solvent for vegetable oil and miscible
.0 with methanol. Thus, it is accepted that solvent may help increases the solubility of methanol and
oil in the reactor and promote transesterification.
A quality improver and environmental friendly system for fast transesterification of Jatropha
curcus oil was developed for the production of biodiesel using a continuous coil flow reactor at
.5 70oC in the presence of a green solvent with potassium hydroxide as a catalyst. When the oil to
methanol molar ratio was 1:5, catalyst concentration 0.75 wt% of oil and flow rate 250 ml/min,
transesterification was completed within 1.62 minute. The purity and conversion of biodiesel was
99.04+0.05% analyzed by the reverse phase HPLC method.
Fig.1. Schematic diagram of continuous tranaesterification of Jatropha curcus oil using coil flow
reactor.
Fig.2. Effect of catalyst concentration and molar ratio (oil to MeOH) on conversion of Jatropha
curcus oil to methyl esters (reaction temp. 70oC, flow rate 250 ml/min).
Fig.3. Effect of solvent concentration and reaction temperature on conversion of Jatropha curcus
oil to methyl esters (catalyst concentration 0.75, molar ratio oil to MeOH 1:5, flow rate 250
ml/min)
Fig.4. HPLC chromatogram of (A) Jatropha Curcus oil showing presence of different
triglycerides. (B) Biodiesel of Jatropha Curcus oil showing presence of different fatty acid methyl
esters.
Fig. 5. Calibration curve of pure standards of (A) MeL and (B) MeO. HPLC condition: UV
detection at 215 nm, injection volumes 5 pL. Other condition as determined in section 3.5.
.0 2. Experimental
2.1. Material
Commercial grades Jatropha curcus oil was procured from local market purchase, methanol
(purity 98%) and KOH (purity 85%) were used from M/S Ranbaxy. According to ASTM the acid
value of the Jatropha curcus oil was 1.3 to 1.8 mg KOH/gm sample. Initial composition of oil
.5 analyzed by HPLC was Triglycerides (TG) 96.5 wt%, Diglycerides (DG) 3 wt% and
monoglycerides (MG) 0.5 wt%. Physico chemical characterization of oil is given in table 1.
2.2. Experimental set-up andprocedure
Experimental set-up for frequently transesterification of Jatropha curcus oil(Pretreated, acid value
0.5) was carried out in a continuous coil flow glass reactor as shown infig 1. Three reservoir A, B
and C were used, reservoir A used to store 10% green solvent (Jatropha curcus biodiesel) diluted
Jatropha curcus oil and another two reservoirs B and C were used to storage two solution of
alcoholic KOH at different concentration 0.50% and 0.25 wt% of oil, respectively. Three peristaltic
pumps P1, P2 and P3 that could run various continuous speeds were used to deliver reactants in insulated reactors. Pump P1 deliver diluted Jatropha curcus oil from reservoir A to reactor first and pump P2 and P3 were used to delivered alkali solution from reservoir B and C to reactor first and third at different flow rate 3 moles and 2 moles, respectively. In this experiment four continuous coil flow reactor are joined in series at different height (inner diameter and length of each coil 5mm ID x 5 meters length). In the coils baffle are fixed in a circular path and distance between the two baffles was 2 cm. Three separating funnels were attached after second, third and fourth reactor, respectively for the separation of glycerol by the downstream process. All coils were immersed in a water condenser type hot glass tube set at 70°C with the help of circulating water bath. In the end product was passed through a condenser at room temp 15°C and finally
.0 product was collected in a collector. The catalyst was removed by warm water washing. The
complete removal of catalyst was checked by phenolphthalein indicator. Tracer of moisture and
unreacted alcohol were removed by vacuum distillation. Finally esters were dried over anhydrous
sodium sulphate and analyzed by HPLC method.
3. Results and Discussion
.5 3.1. Catalysttype and concentration
Catalyst used for the transesterification of vegetable oils are classified as alkali, acid, enzyme
and heterogeneous catalysts, among of which alkali catalysts like sodium hydroxide, potassium
hydroxide and potassium methoxide are more effective. If the oil has high FFA and water content
acid catalyzed transesterification is suitable. As a catalyst in the process of alkaline methanolysis
mostly sodium hydroxide or potassium hydroxide has been used when the oil has less than 1%
The typical present work continuous transesterification of Jatropha curcus oil, alkaline catalyst
is more suitable due to the presence of low FFA. In the methanolysis of Jatropha curcus oil with potassium hydroxide gives the best results. In this process flow rate was 250 ml/min, temperature
70°C and molar ratio oil to methanol 1:5 was held constant, fig. 2 summarized the effects of
variation in catalyst concentration from0.25 to 1.0 wt% of oil. Optimization of catalyst percentage:
when catalyst percentage was 0.25% gives 75% conversion biodiesel, after increasing the catalyst
percentage the conversion was increased at 0.75 wt% catalyst (KOH) gives the best conversion
99.04 0.05%. There are many drawbacks in the excessive use of alkaline catalyst in the
transesterification reaction. Higher catalyst concentration increases the solubility of methyl esters
in the glycerol phase of the final product. As a result, a significant amount of methyl esters remain
in the glycerol layer after the phase separation.
.0 3.2. Molar ratio
One of the most important variables affecting the yield of ester is the molar ratio of alcohol to
oil. The stoichiometric ratio for transesterification required three moles of alcohol and one mole
of triglyceride to yield the three moles of fatty acid methyl esters and one mole of glycerol.
However, transesterification is a reversible reaction in which a high molar ratio is used to drive
.5 the reaction to the forward direction, enhance the solubility and to increase the contact between
the triglycerides and alcohol molecule. Experiments were conducted with molar ratios of oil to
methanol 1:3, 1:4, 1:5 and 1:6 for catalyst concentration 0.75 wt% of oil. The experimental data
are presented in Fig. 2. In the present work at the molar ratio 1:5 the conversion of triglycerides
was maximum > 99%. In this experiment methanol feeds in two parts 3 moles and 2 moles in
reactor first and third, respectively. Molar ratio shows no effect on acid, peroxide, saponification
and iodine values of methyl esters (Tomasevic et al., 2003). However, the high molar ratio of
alcohol to vegetable oil interferes with the separation of glycerol because there is an increase in
solubility.
3.3. Effect of reaction temperature
The conversion of Jatropha curcus oil in to fatty acid methyl esters increases with reaction
temperature. Experimental trials were carried out at 25°C (room temperature), 65°C, 70°C and
75°C. In all experiments oil to methanol ratio was constant 1:5 and 0.75 wt% KOH (as catalyst)
were used (the optimal condition achieved in the previous section). The yield of methyl ester at
room temperature and 65°C were 42% and 92%, respectively. The maximum conversion >99% is
obtained at the temperature 70°C. Fig. 3 indicates the results of these experiments; methanolysis
of vegetable oil is normally performed near the boiling point of the alcohol.
3.4. Effect offlow rate
.0 In the process of continuous transesterification of Jatropha curcus oil experiments were
optimized at total flow rate ranging from 200 ml/min to 275 ml/min, all experiments were
conducted with catalyst concentration 0.75 wt% of oil, molar ratio of oil to methanol 1:5 and
reaction temperature 70°C (the optimal condition achieved in the previous sections). The effects
of total flow (oil+MeOH) rate and residence time are given in table 2, when the total flow rate of
.5 oil and MeOH was 250 ml/min (207 ml oil and 43 ml MeOH). It gives the best conversion >99%
and production of biodiesel was 13.17 L/hr.
3.5. Effect ofgreen solvent concentration
The influence of solvent on fatty acid methyl esters (FAMEs) yield is shown infig.3. The
experimental trials were carried out at different concentration of green solvent (biodiesel). The
maximum fatty acid methyl esters yield could be obtained at the concentration of solvent 7wt% of
oil. Biodiesel is a good solvent for vegetable oil and miscible with methanol. Thus, it is expected
that biodiesel may help mix methanol and oil in the reactor coils and increase rate of reaction.
3.5. HPLCAnalysis
HPLC was used to analyze the purity, conversion and FAMEs composition of the biodiesel
esters sample. The Reverse phase high performance liquid chromatography (RP-HPLC) separates
different components according to their polarity. The chromatographic apparatus consisted of a
model waters 600 pump with waters 600 controller, waters 2,996 photodiode array detector, a
nova-pack, 3.9 x 150 mm column with guard column of dimension 3.9 x 20 mm, both packed
with C18 particle with diameter 4 im. (all from waters, Milford MA, USA).
HPLC condition: RP-HPLC method flow rate of iml/min, an injection volume of5pl, a column
temperature of 45 °C, the UV detection at 215 nm and a 40 min gradient mobile phase 15% H 2 0
+ 85% CH 30H in 10 min, 100% CH 30H in 0 min, 60% CH3 0H + 15% hexane + 25% propane
.0 2o1 in 30 min and for the last 10 min system back to initial state 15% H 2 0 + 85% CH30H were
used for the separation and determination of the compound produced during the methanolysis of
Jatropha curcus oil in all the experiments Fig. 4 shows the HPLC separation of oil (A) and
biodiesel (B), respectively. The fatty acids compositions of Jatropha curcus oil are given in Table
3.
.5 Calibration curves were generated for two standards (Sigma Aldrich) methyl oleate and methyl
linoleate. Each data point was obtained from at least two repeated measurements. Stock solutions
of the standards were prepared as about 5 mg/ml in hexane, and then serial dilution were made as
required. Relative integrated peak area versus injected amount of the methyl ester standard was
plotted for MeO and MeL. The calibration curves (relative peak area versus concentration are
shown in Fig. 5) of the standards showed good linearity (R 2 =0.999).
4. Characterization
4.1. Kinematic Viscosity, Acid number and oxidation stability
All the physicochemical properties are given in Table 4. The kinematic viscosity of biodiesel
at 40°C was determined following ASTM D 445 using a Rheotek AKV 800 automated kinematic
viscometer (Poulten Selfe and Lee Ltd., Essex, England). The acid number of biodiesel was
determined according to ASTM D 664 using a Brinkman/Metrohn 809 Titrando (Westbury, NY).
The oxidation stability of biodiesel was determined as the induction period (IP) according to EN
14112 using a Metrohn 743 Rancimat instrument (Herisau, Switzerland).
4.2. Coldflow properties
The cloud point (CP), pour point (PP) and cloud filter plugging point (CFPP) measurements
were done as per ASTM standers, D 2500-05, D 97-96a and D 6371-05 , respectively .A Lawler
.0 model DR-34H automated cold properties analyzed (Lawler Manufacturing Corporation, Edison,
NJ) was used to measure the cold flow properties.
Conclusion
The present study results indicate that the optimum reaction condition for frequently
methanolysis of Jatropha curcus oil using coil flow reactor i.e., 0.75% KOH as catalyst (wt% of
.5 oil), reaction temperature 70°C, oil/methanol molar ratio 1:5 and residence time 1.62 min gives
>99% conversion and production of biodiesel 13.17 L/hr. The synthesized biodiesel match ASTM
and BIS specification (table 4). The purity and quality of synthesized biodiesel were checked by
the HPLC methode.
Table 1. Physico chemical characterization of Jatropha curcus oil.
Density at 15°C 0.918 gm/cm3
Refractive index (nD 40'C) 1.484
Molecular weight 888
Kinematic viscosity at 40°C 34.33 c St
Saponification value 199 mg KOH/gm oil
Acid value 0.5 mgKOH/gm oil (after pretreatment of oil)
Cetane number 23
Flash point 186
Table 2. Effect of flow rate and residence time on yield of Jatropha curcus oil to methyl esters. (Molar ratio oil to methanol 1:5, catalyst concentration 0.75 wt% of oil, reaction temperature 70 C). Flow rate (ml/min) Residence time (min) Conversion
% Oil MeOH Total Reactor Reactor Reactor Reactor Tota Sl S2 S3 (ml) (ml) (ml) (RI) (R2) (R3) (R4) 1 166 34.38 200.38 0.52 0.52 0.49 0.49 1.93 61.5 97.0 99.4 0 186. 38.63 225.13 0.46 0.46 0.43 0.43 1.73 60.5 96.8 99.4 5 1 207 42.88 249.88 0.42 0.42 0.39 0.39 1.62 60.2 96.8 99.4 1 228 47.23 275.23 0.38 0.38 0.35 0.35 1.48 45.8 80.0 85.6 0 S = Separating funnel First, S2 = Separating funnel second, S3 = Separating funnel third.
Table 3. Fatty acid methyl esters (FAME) composition of Jatropha curcus oil based biodiesel.
Fatty acid Percentage
Palmitic (C16) 15.82
Linolenic (C18:3) 0.73
Linoleic (C18:2) 30.56
Oleic (C18:1) 44.21
Stearic (C18:0) 8.15
Table 4. Physico chemical characterization of Jatropha curcus biodiesel.
Property ASTM ASTM BIS Biodiesel method Specification Specification
Viscosity 40°C (mm2 /s) D 445 1.9-6.0 2.5-6.0 3.88
Acid number (mgKOH/g) D 664 0.5 <0.5 0.18
Free glycerin (mass %) D 6584 0.020 ---- 0.008
Total glycerin (mass %) D 6584 0.24 ---- 0.24
Oxidation stability (IP, h) EN 14112 3 minimum ---- 5.0
Cloud point D 2500-05 -3 to +12 ---- -5
Pour point D 97-96a -15 to +10 ---- -12
Cetane number D 613 >47 >51 54
Cold filter plugging point D 6371 -4 to -9 ---- -1
Density at 15°C (Kg/m3) D 976 0.575 to 0.900 0.860-0.900 0.8633
Flash point (°C) D 93 >100 >120 135
Carbon residue (wt%) D 4530 <0.02 <0.02 0.005
Copper strip corrosion D6751 <No. 1.0 1.0 1.0
(3 hrs at 100°C)
Water content (ppm) D 95 <500 <500 230
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ASTM D 445-06., 2006. Standard test method for kinematic viscosity of transparent and opaque
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Claims (5)
1. A method of transesterification of Jatropha curcus oil, alkaline catalyst is more suitable due to
the presence of low FFA.
2. The method as claimed in claim 1, wherein in the methanolysis of Jatropha curcus oil with
potassium hydroxide gives the best results.
3. The method as claimed in claim 1, wherein in this process flow rate was 250 m/min,
temperature 70°C and molar ratio oil to methanol 1:5 was held constant.
4. The method as claimed in claim 1, wherein the effects of variation in catalyst concentration
from 0.25 to 1.0 wt% of oil; and Optimization of catalyst percentage: when catalyst percentage
was 0.25% gives 75% conversion biodiesel, after increasing the catalyst percentage the
conversion was increased at 0.75 wt% catalyst (KOH) gives the best conversion 99.04 0.05%.
Fig.1. Schematic diagram of continuous tranaesterification of Jatropha curcus oil using coil flow reactor.
Fig.2. Effect of catalyst concentration and molar ratio (oil to MeOH) on conversion of Jatropha curcus oil to methyl esters (reaction temp. 70oC, flow rate 250 ml/min).
Fig.3. Effect of solvent concentration and reaction temperature on conversion of Jatropha curcus oil to methyl esters (catalyst concentration 0.75, molar ratio oil to MeOH 1:5, flow rate 250 ml/min)
(A)
(B)
Fig.4. HPLC chromatogram of (A) Jatropha Curcus oil showing presence of different triglycerides. (B) Biodiesel of Jatropha Curcus oil showing presence of different fatty acid methyl esters.
(A)
(B)
Fig.
5. Calibration curve of pure standards of (A) MeL and (B) MeO. HPLC condition: UV detection at 215 nm, injection volumes 5 µL. Other condition as determined in section 3.5.
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