Biodiesel production from crude tall oil

Production of biodiesel from crude tall oil (CTO)

S. Marda, S.Omori, S. Shastri and S. G. Chatterjee Paper and Bioprocess Engineering SUNY-ESF Syracuse, NY Date: February 14, 2007

Overview  Introduction  Production of biodiesel from crude tall oil  Characterization of biodiesel  Conclusions  Future work

Introduction

Introduction  What is biodiesel?  Why biodiesel?  Depletion of resources  

Half of the world’s oil resources will be exhausted by 2025 (EIA) Global oil production will peak in next 10 years

 Environmental concerns  Advantages of biodiesel       

Biodegradable Renewable Non-toxic, thus safe handling and transporttion Reduction of greenhouse gas emissions Reduction in particulates Can produce domestically High cetane number

 Disadvantages of biodiesel 

Increase in NOx emissions

Introduction  Objective 

Investigate the feasibility of producing biodiesel from CTO

 Relevance of study    

Annual global production of tall oil was 1.6 million metric tonnes in 2000 Conventionally converted to tall oil rosin, varnishes, tall oil fatty acids by tall oil fractionators Recently inventory build-up at fractionators due to weak demand of products derived from CTO Very viscous, malodorous and sticky  Makes transportation very cumbersome



CTO sells at very low price( ~ $0.10- 0.35 per kg)

Production of biodiesel from crude tall oil

Production of biodiesel from crude tall oil

Introduction  With both Northern CTO (NCTO) and Southern CTO (SCTO)  Using acetyl chloride and methanol in closed vessel  Using sulfuric acid and methanol in closed vessel  Using sulfuric acid and methanol by the condenser method  With molecular sieve  Without molecular sieve

Production of biodiesel from crude tall oil

By the acetyl chloride-methanol method  Experiment  150 g of SCTO/NCTO  Varying amount of methanol  Different molar ratios of acetyl chloride to fatty acids

 Assumed molecular weight of 290  Temperature 55 C

 Extraction  With ethyl acetate

 Vacuum distillation  Under pressure of 2 mm Hg

 Quantification  Weight % - By direct weighing

Production of biodiesel from crude tall oil

By the acetyl chloride-methanol method Yield

of

biodiesel

produced

from

NCTO

and

SCTO

by

the

acetyl

chloride-methanol

method

Source

Amount of acetyl chloride (ml)

Amount of methanol (ml)

Reaction time (hours)

Temperature ( C)

Yield of biodiesel (wt %)

NCTO (Na)

100

600

24

25

29.9

NCTO (Na)

100

600

1

55

25.2

NCTO (Na)

100

600

6

55

36.9

SCTO

100

600

1

25

52.7

SCTO

100

600

6

25

52.7

SCTO

100

600

1

55

65.9

SCTO

100

600

6

55

66.0

SCTO

10

350

1

55

60.6

SCTO

10

350

6

55

55.7

SCTO

10

350

0.5

55

56.1

SCTO

3

350

1

55

56.8

SCTO

3

150

1

55

55.9

SCTO

1

50

1

55

54.9

VO

100

350

1

55

88.5

Production of biodiesel from crude tall oil

By the sulfuric acid-methanol method Yield of biodiesel produced from NCTO and SCTO using H2SO4 and methanol

Source

SCTO

SCTO

SCTO

SCTO SCTO SCTO NCTO (H)

Type

Closed reaction flask Closed reaction flask Condenser (with molecular sieve) Condenser (with molecular sieve) Condenser Condenser Condenser

Amount of sulfuric acid (ml)

Amount of methanol (ml)

Reaction time (hours)

Temp. ( C)

Yield of biodiesel (wt%)

3

350

1

55

52.9

3

350

6

55

60.5

3

350

1

65

55.4

3

350

6

65

55.8

3 3 3

350 350 350

6 20 20

65 65 65

57.4 56.7 46.1

Production of biodiesel from crude tall oil

Biodiesels produced from SCTO, NCTO and VO using the acetyl chloride and sulfuric acid method

Characterization of biodiesel

Characterization of biodiesel  Introduction  To evaluate product quality  To compare with other diesel and biodiesel products

 Properties    

Density Viscosity Heating Value Composition

Density  Introduction  Mass per unit volume  Low density desired for biodiesel

 Measurement procedure  Weighing 1 ml of biodiesel  ρ = m/v ρ = density of biodiesel, g/cm3 m = mass of biodiesel, g v = volume of biodiesel, cm3

Density Results and discussion Type of Biodiesel

Temp. ( C)

Yield of biodiesel (wt %)

Density of biodiesel (g/cm3)

NCTO (Na),1:3, 24 h NCTO (Na),1:3,1 h NCTO (Na),1:3, 6 h SCTO,1:3, 1 h SCTO,1:3, 6 h SCTO,1:3, 1 h SCTO,1:3, 6 h SCTO,1:0.3, 1 h SCTO,1:0.3, 6 h SCTO, Sulfuric acid,1 h SCTO, Sulfuric acid, 6 h VO (Acetyl Chloride) VO (Transesterification) WVO(Transesterification) Chicken Fat(Transesterification) Bacon Fat(Transesterification) Beef Fat(Transesterification)

25 55 55 25 25 55 55 55 55 65 65 55 65 65 65 65 65

29.9 25.2 36.9 52.7 52.7 65.9 66.0 60.6 55.7 52.9 60.5 88.5 97.7 81.7 81.7 84.5 86.3

0.921 0.920 0.924 0.844 0.840 0.914 0.949 0.928 0.934 0.879 0.946 0.926 0.905 0.887 0.904 0.935 0.929

Note: 1:3 or 1:0.3 are molar ratios of tall oil to acetyl chloride and 1 h, 6 h and 24 h are hours of reaction

Viscosity  Introduction  An internal property of a fluid that is a measure of resistance to the flow of the fluid  Dynamic viscosity [ ]  poise

 Kinematic viscosity [ ]  measure of resistive flow of a fluid under the influence of gravity  stokes

Viscosity Measurement procedure  Viscometer

 U-shaped tube with capillary and glass bulb  Principle  Usage of std. fluid (Biodiesel)

(Standard)

T (Biodiesel) T (Standard)

(Biodiesel) (Standard)

T (Biodiesel) T (Standard)

= kinematic viscosity of biodiesel, cm2/s = kinematic viscosity of standard fluid, cm2/s = time taken by biodiesel to flow through capillary, s = time taken by standard fluid to flow through capillary, s

Viscosity Results and discussion

Description of type of Biodiesel

NCTO (Na),1:3, 24 h NCTO (Na),1:3,1 h NCTO (Na),1:3, 6 h SCTO,1:3, 1 h SCTO,1:3, 6 h SCTO,1:3, 1 h SCTO,1:3, 6 h SCTO,1:0.3, 1 h SCTO,1:0.3, 6 h SCTO, Sulfuric acid,1 h SCTO, Sulfuric acid, 6 h VO (Acetyl Chloride) VO (Transesterification) WVO(Transesterification) Chicken Fat(Transesterification) Bacon Fat(Transesterification) Beef Fat(Transesterification)

Temp. ( C)

Yield of biodiesel (wt %)

Density of biodiesel (g/cm3)

Viscosity of biodiesel (cm2/s)

25 55 55 25 25 55 55 55 55 65 65 55 65 65 65 65 65

29.9 25.2 36.9 52.7 52.7 65.9 66.0 60.6 55.7 52.9 60.5 88.5 97.7 81.7 81.7 84.5 86.3

0.921 0.920 0.924 0.844 0.840 0.914 0.949 0.928 0.934 0.879 0.946 0.926 0.905 0.887 0.904 0.935 0.929

8.70 7.61 8.46 9.90 10.91 13.98 12.75 10.62 9.51 10.14 11.93 10.28 6.87 7.06 9.05 9.85 8.95

Note: 1:3 or 1:0.3 are molar ratio of tall oil to acetyl chloride and 1 h, 6 h and 24 h are hours of reaction

.

Heating Value  Introduction  Heat of combustion  Energy released (combustion with oxygen)  Measured by ASTM procedures

 Measurement procedure  Empirical/approximate method  Based on comparison  Amount of fuel consumed to raise temp of water from 30 C to 80 C

Heating Value Results and discussion

Fuel

Fuel consumed in process of heating from 30 C to 80 C, g

Commercial Diesel Biodiesel from SCTO

0.357 0.357 0.414 0.412

Average Heat of heat of combustion combustion (HHV), BTU/lb BTU/lb 19673* 19673* 19673* 16960 16993 17025

* Source: - Petroleum-based fuels property database, National Renewable Energy Laboratory (NREL)

Composition  Introduction  To quantify product  To find out reasons for differences between different biodiesels and raw materials

 Measurement procedure    

Using Gas Chromatography (GC) Using internal standard and standard methyl esters Factor calculation Comparing sample peaks with respective standard peaks

Composition

Figure 6.1: Standard peaks using standard methyl esters

Figure 6.6: Biodiesel from vegetable oil (transesterification method)

Figure 6.4: Biodiesel from SCTO (acetyl chloride and methanol method)

Figure 6.3: Biodiesel from NCTO (soap skimmed form)

Composition of biodiesel Description of type of Biodiesel

Methyl palmitate (wt%)

Methyl linoleate (wt%)

Methyl oleate (wt%)

Methyl stearate (wt%)

Total (wt%)

NCTO (Na),1:3, 24 h, 25 C NCTO (Na),1:3,1 h, 55 C NCTO (Na),1:3, 6 h, 55 C SCTO,1:3, 1 h, 25 C SCTO,1:3, 6 h, 55 C SCTO,1:3, 1 h, 55 C SCTO,1:3, 6 h, 55 C SCTO,1:0.3, 1 h, 55 C SCTO,1:0.3, 6 h, 55 C SCTO, Sulfuric acid,1 h, 65 C SCTO, Sulfuric acid, 6 h, 65 C VO (Acetyl Chloride) VO (Transesterification) WVO(Transesterification) Chicken Fat(Transesterification) Bacon Fat(Transesterification) Beef Fat(Transesterification)

8.3 7.8 7.5 6.3 6 4.9 4.8 4.5 5.6 6.2 5.7 9.1 8.6 5.7 21.8 30.4 25.3

49.4 46.1 45.1 33.5 30.8 27.2 24.7 22.6 27.8 31.5 30.9 53.8 54.1 35.8 14.4 6.5 0

6.6 6.3 6.2 33.9 31 26.7 24.2 22.7 27.4 31.3 31.7 20.4 19.9 52.8 33.5 46.5 27

2.2 2 2 2 1.6 1.3 1.1 1.2 1.6 1.7 1.8 3.2 2.9 5.5 4.9 16 15.4

66.5 62.2 60.8 75.7 69.4 60.1 54.8 51.0 62.4 70.7 70.1 86.5 85.5 99.8 74.6 99.4 67.7

Note: 1:3 or 1:0.3 are molar ratios of tall oil to acetyl chloride and 1 h, 6 h, and 24 h are hours of reaction.

Conclusions  Biodiesel can be produced from CTO  SCTO gives higher yield than NCTO  Acidified as well as soap skimmed form can be used for NCTO  Can be produced at temperatures: 25 C,35 C,45 C,55 C  Closed reaction produces better results  Strong acidic condition is critical  Acetyl chloride or sulfuric acid can be used  Speculation: Any other strong acid can be used  Biodiesel from VO can be produced by acetyl chloride-methanol method can  Produced biodiesel has similar properties  Density, viscosity, heating value, etc.

Conclusions  We postulate following reaction RCOOH + CH3OH + Acid

Methanol

CH3COCl Acetyl chloride

RCOOCH3 + CH3COOH + HCl Ester

Acetic acid

 MO,MP,ML, and MS major compound of any biodiesel  Comprise more than 50% of the total biodiesel

Hydrochloric acid

Future work  Kinetics and mechanism of biodiesel production from SCTO and/or NCTO using acetyl chloride and methanol  Kinetics and mechanism of biodiesel production from SCTO and/or NCTO using sulfuric acid and methanol  Exploration of various pathways to utilize resin acids of tall oil to produce any valuable material such as fuel, wax, varnishes etc  Conversion of batch process into a continuous one  Pilot scale study of production of biodiesel from tall oil using acetyl chloride/sulfuric acid and methanol  Characterization of the biodiesels produced by measuring some more properties and their comparison with those of commercial diesel

Acknowledgements SUNY-ESF  Financial support

Thank you.

Questions

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