Submitted by : Arun Nagarajan

Renewable energy

Production and selected fuel properties of biodiesel from promising non-edible oils

Rui Wang, Milford A. Hanna

2

Biodiesel - Introduction

Fossil fuel : non renewable resource – million year.

But depleted – faster than regenerated.

Biodiesel - Alternative fuel for diesel engines.

Made from vegetable oil or animal fat.

Meets health effect testing (CAA).

Lower emissions, High flash point (>300F), Safer.

Biodegradable, Essentially non-toxic.

Reduces carbon monoxide, hydrocarbon, and sulfur emissions.

(Ma and Hanna, 1999)

3

Environmental Issues

Combustion of fossil fuels - ↑ atmospheric CO2 level. Fossil fuels are a limited resource.

Edited from: http://www.gift-n-garden.com/algae_biodiesel.jpg

Biodiesel’s Closed

Carbon Cycle

4

Reason for study

95% Biodiesel produced from EDIBLE OIL.

Leads to imbalance between Food & Energy resource.

So overall production cost is HIGH (> fossil fuel).

To promote global commercialization.

LOW COST, NON-EDIBLE OIL

Jatropha curcus, Madhuca indica – best feed stock.

• High monounsaturated fatty acid (C16:1; C18:1)

• Low polyunsaturated fatty acid (C18:2, C18:3)

• Saturated fatty acids (C16:0, C18:0).

Superior character

of Non-edible oil

Hence Non-edible oil is preferred (Knothe, 2009; Ramos et al., 2009)

5

About feed stock

Feed stock – Euphorbiaceae – significant amount of oil.

Euphorbia lathyris L. (EL) - (Potential source of petroleum crop)

Sapium sebiferum L. (SS) - (Potential source of petroleum crop)

Jathropha curcas L. (JC) – (Accepted species for biodiesel)

Jathropha Curcas Euphorbia lathyris Sapium sebiferumReference: Janick and Paul, 2008; All image sources : http://www.kinmatsu.idv.tw/

6

About crops

Euphorbia lathyris L. Sapium sebiferum L. Jatropha curcas L.

• Erect biennial plant.

• Native: South Europe, Africa

and Asia.

• Grow in drought, frost and

arid soil.

• Yield 1.5-2.5 tons/ha/year –

oil content 48.0% of seed

weight.

• Perennial woody plant.

• Native: East Asia, China &

Japan.

• Grow in alkaline, saline,

droughty and acidic soil.

• Yield 4-10 tons/ha/year (seeds)

– oil content 12-29% of seed

weight.

• Perennial plant.

• Native: American tropic,

Mexico.

• Drought and aridity

resistance.

• Yield 3.5 tons/ha/year -

Seeds contain 27-40% oil.

Ayerbe et al., 1984; Ratti et al., 1995; Gu and Liu, 2001; Janick and Paul, 2008)

7

Drawback

Non-edible oil:

Cannot directly transesterified – basic catalyst.

Reason: High content of fatty acids. (Pinzi et al., 2009)

Hence two-step catalytic process.

Pre-esterification

Transesterification

This two-step process was already involved in J. curcus

production (Pinzi et al., 2009).

8

FAC & FAME contents

EL oil & JC oil – Mechanical expression.

SS kernel oil – De waxing and crushed to extract oil. (Rajam et al., 2005)

Extracted OIL + KOH + Boron tri fluoride Methylated esters

Major fatty acid components were identified by GC/MS.

Methylated esters

Boron tri

fluoride

KOHOIL

Agilent GC6890 with HP-innowax and

flame ionization detector is used.

Yield of FAME:

X 100%

FAME is not Biodiesel unless it meets the relevant

standards.

9

Production & purification

Oil bath(600RPM)60.0±0.3˚C

Stirred

50g Oil

MethanolSulphuric

acid Product (Pre treated oil)

Oil bath(600RPM),

60.0±0.3˚C, 30min

Pretreated oil

Methanol

KOH-CH3OH

Cooled &Allowed to settle

Se

pa

ratin

g c

olu

mn

Allowed to

settle

In separa

ting fu

nnel

Se

pa

ratin

g c

olu

mn

Bio Diesel

10

Results

FAC (wt.%) ELO DSSKO JCO

Proportion of saturation (Cn: 0) 8.76 7.58 18.63

Proportion of monounsaturation (Cn: 1) 82.66 18.08 42.47

Proportion of polyunsaturation (Cn: 2,3) 6.49 72.79 37.21

Degree of unsaturation 95.64 163.66 116.89

Table 1: The Fatty acid composition (FAC) of three oils

Property Limits EL DSSK JC

Fame content (wt.%) 96.5 min 97.61 98.03 98.27

Cetane number 51 min 59.6 40.2 55.4

Oxidation stability (110˚C, h) 6min 10.4 0.8 8.0

Water content (mg/kg) 500 max 400 300 Traces

Flash point (˚C) 120.0 min 181 180 147

Table 2: Properties of the biodiesels from three oils (EN 14214)

11

Discussion

ELO possessed the

Highest monounsaturated fatty acid content (82.66 wt.%)

Lowest polyunsaturated fatty acid content (6.49 wt.%)

Low saturated fatty acid content (8.78 wt.%)

High oxidative stability (10.4h)

High Cetane number (59.6)

Although cetane number (59.6) of ELO biodiesel was lower than palm oil

(61) (Rashid et al., 2008)

Good cold flow properties

12

Discussion (Cont…)

(a) Effect of catalyst conc. on

esterification reaction.

In which conc. Was optimized

at 0.8, 0.4, 0.4 wt. % for ELO,

DSSKO and JCO.

(b) The effect of the

methanol to oil ratio on

esterification reaction.

Optimum result for ELO,

DSSKO and JCO were

achieved within 1hr at 10:1,

8:1, 8:1 respectively.

(c) Effect of reaction time on

esterification.

15, 30, 45, 60 min were

evaluated. In which 45, 30, 30

were optimum for ELO,

DSSKO and JCO respectively.

(d) The effect of catalyst

(KOH) concentration on

transesterification.

FAME yields of 85.6%, 86.3%

and 84.2% were obtained from

ELO, DSSKO and JCO.

13

Conclusion

Comparatively low cetane number (55.4), oxidative stability (8h) of JCO

biodiesel were considered moderate biodiesel. (Table 2)

Alternatively, low cetane number (40.2), oxidative stability (0.8h) were

observed in DSSK biodiesel is due to low degree of saturation (7.58%) and

high degree of polyunsaturation (72.79%) and it did not satisfy standards.

The ELO and JCO biodiesels fits EN 14124 standard.

The fuel properties of ELO biodiesel were superior than other fuels.

Thus E. lathyris L. is promising species for biodiesel feed stock and

potential substitute for J. curcas L.

14

My view

In my view, Competition of edible oil sources as food vs. fuel makes

edible oil not an ideal feedstock for biodiesel production.

Instead, Waste edible oil should be made the primary source for

biodiesel feedstock due to its abundant availability. Fresh edible and

non-edible oils can then be used to supplement the shortfall of WEO

as feedstock.

Recommended source for waste edible oil are:

Industrial deep fryers in potato processing plants, snack food factories

and fast food restaurants.

15

References

Ma, F.R., Hanna, M.A., 1999. Biodiesel production: a review. Bioresour. Technol. 70, 1–15. Knothe, G., 2009. Improving biodiesel fuel properties by modifying fatty ester composition.

Energy Environ. Sci. 2, 759–766. Janick, J., Paul, R.E., 2008. Encyclopedia of Fruits and Nuts. CABI, London. Ayerbe, L., Tenorio, J.L., Ventas, P., Funes, E., Mellado, L., 1984. Euphorbia lathyris as an energy

crop-part 1. Vegetative matter and seed productivity. Biomass 4, 283–293. Ratti, N., Sidhu, O.P., Behl, H.M., 1995. Quantification of polyisoprenes from some promising

euphorbs. Bioresour. Technol. 52, 231–235. Gu, Q., Liu, J., 2001. The analysis of correlation between ratio of different parts and their oil

contents of Sapium sebiferum seed and environmental factors. J. Plant Resour. Environ. 14, 14–16. Pinzi, S., Garcia, I.L., Lopez-Gimenez, F.J., Luque de Castro, M.D., Dorado, G., Dorado, M.P., 2009.

The ideal vegetable oil-based biodiesel composition: a review of social, economical and technical implications. Energ. Fuel 23, 2325–2341.

Rajam, L., Soban Kumar, D.R., Sundaresan, A., Arumughan, C., 2005. A novel process for physically refining rice bran oil through simultaneous degumming and dewaxing. J. Am. Oil Chem. Soc. 82, 213–220.

Rashid, U., Anwar, F., Moser, B.R., Knothe, G., 2008. Moringa oleifera oil: a possible source of biodiesel. Bioresour. Technol. 99, 8175–8179.

16

Thank you