characterization of minor components in biodiesel from non...

Luiz Ramos

4th CISB Annual Meeting

São Paulo, SP – Nov 2014Química - UFPR

CEPESQ

Luiz Pereira RamosChemistry, Federal University of Paraná (UFPR)

www.quimica.ufpr.br/cepesq, [email protected]

Nelson Roberto Antoniosi FilhoChemistry, Federal University of Goiás (UFG)

[email protected], http://lames.quimica.ufg.br

Characterization of minor components in

biodiesel from non-conventional sources

Química - UFPR

CEPESQ

Luiz Ramos



CEPESQ

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Luiz Ramos



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Currently, 58 industrial production plants are authorized by ANP to produce biodiesel in Brazil

The total authorized production capacity is 21,046.79 m3/day (7.15 TPY of 340 days) plus 1.042,72 m3/day (0.35 TPY) from units that are either under construction or being expanded (nearly 5% of the current authorized production capacity)

New biodiesel standard released in August 25, 2014 with adjustments in the limits for oxidation stability and both water and monoacylglyceride contents

Mandatory use boosted to B7 in November 01, 2014

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ANP Authorized Annual Production Capacity

Monthly compulsory demand for biodiesel

Monthly biodiesel production

Luiz Ramos



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73.72

20.29

4.04

0.01

0.471.01

0.46

Soybeans

Beff tallow

Cottonseed

Chicken fat

Lard (pig fat)

Used frying oil

Other materials

5

Luiz Ramos



CEPESQPROPERTY UNIT LIMIT

METHOD

ABNT NBR EN/ISO

Aspect - LII - -

Specific gravity at 20 °C kg/m³ 850 a 900 7148, 14065 EN ISO 3675 & 12185

Kinematic viscosity at 40 °C mm²/s 3,0 a 6,0 10441 EN ISO 3104

Water, max. mg/kg 200,0 - EN ISO 12937

Total contamination, max. mg/kg 24 15995 EN 12662

Flash point, min. °C 100,0 14598 EN ISO 3679

Total ester content, min % massa 96,5 15764 EN 14103

Sulfated ashes, max. % massa 0,020 6294 EN ISO 3987

Total sulfur, max. mg/kg 10 15867 EN ISO 20846, 20884

Sodium + Potassium, max. mg/kg 5 15554, 15555, 15553, 15556 EN 14108, 14109 & 14538

Calcium + Magnesium, max. mg/kg 5 15553, 15556 EN 14538

Phosphorus, max. mg/kg 10 15553 EN 14107, 16294

Copper corrosivity, 3h at 50 °C, max. - 1 14359 EN ISO 2160

Cetane number - Anotate - EN ISO 5165

CFPP, max. °C (9) 14747 EN 116

Acid number, max. mg KOH/g 0,50 14448 EN 14104

Free glycerol, max. % massa 0,02 15771, 15908 EN 14105, 14106

Total glycerol, max. % massa 0,25 15344, 15908 EN 14105

Monoacylglycerol, max. % massa 0,70 15342, 15344, 15908 EN 14105

Diacylglycerol, max. % massa 0,20 15342, 15344, 15908 EN 14105

Triacylglycerol, max. % massa 0,20 15342, 15344, 15908 EN 14105

Methanol and/or Ethanol, max. % massa 0,20 15343 EN 14110

Iodine number g/100g Anotate - EN 14111

Oxidation stability at 110 °C, min. h 8 - EN 14112, EN 15751

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Poor cold flow properties Poor oxidative stability

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http://www.therenewableplanet.com/photos/renewable_planet_images/picture159345.aspx

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RBTB – Brazilian Network for Biodiesel Technologies

Five main strutural areas of R&D: Feedstock, Production, Use of Coproducts, Storage and Handling, and Characterization

Nearly 37 specialized and highly skilled laboratories were equipped by MCTI to give full support to the rapid development of the Brazilian biodiesel production chain

Several research groups were funded mostly by MCTI to develop solutions for the entire biodiesel production chain

High scientific and technological productivities were achieved

Highly trained human resources were formed

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CEPESQ

HO

β-Sitosterol

Cholesterol

HO

Sphingolipids

Cerebrosides

R is a fatty acid

O

CH2OH

OH

OH

OH

O

HN

OH

R

O

H3C(CH2)12CH CH CH CH2OPOCH2CH2N(CH3)3

OH NH O

COR

O

Phospholipids

H2C O

CO H

OH2C

C

O

R1

C

O

R2

P O

O

X

O-

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Sterol glycosides

Free sterols

Acylated sterol glycosides

Esterified sterols

Sterol and sterol derivatives:

o Important for the traceability of

biodiesel sources

o Poor cold flow properties (high

cloud point)

o Partly responsible for deposits

during storage of “on spec” fuels

o May cause deposits in the diesel

engine as well

o May cause coking at the injector

nozzle

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CEPESQ

Sterol glycosides

12

catalyst

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Bezerra and Antoniosi Filho, Fuel 130 (2014) 149–153

GC-FID of free steroids present in commercial biodiesel and soybean biodiesel

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Unrefined soybean oil Refined soybean oil

Campesterol (A)

Stigmasterol (B)

β-Sitosterol (C)

Biodiesel from unrefined soybean oil Biodiesel from refined soybean oil

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Bezerra and Antoniosi Filho, Fuel 130 (2014) 149–153

GC-FID of free steroids present in commercial biodiesel and soybean biodiesel

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CO

TT

ON

RA

PE

PE

AN

UT

MO

RIN

GA

SO

YB

EA

NS

SU

NF

LO

WE

R

CH

ICK

EN

FA

T

BE

EF

TA

LL

OW

PA

LM

IST

E

BA

BA

SS

U CR

AM

BE

PA

LM

CA

ST

OR

CO

RN

oils and fatsbiodiesel

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Crude soybean oil

Refined soybean oil

GC-FID Analysis of Free Sterols

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Sterol Glucoside Content in Vegetable

Oils as a Risk for the Production of

Biodiesel – Study of the Technological

Chain Impact – OVDI-ASA

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Untreated biodieselGC-FID analysis of free

sterols before and after

adsorption and filtration

Biodiesel treated with

acid-activated Bauxite

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CEPESQ

C C

H H

(CH2)4 CH2H3C

C C

(CH2)7

H H

C

O

O CH3

C

(CH2)4H3C

C

CH2

C C

(CH2)7

HO OH

C

O

O CH3

O

Oxidation

Biodiesel stability

C C

H H

(CH2)4 CH2H3C

C C

(CH2)7

H H

C

O

OH

Microbes / Water

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CEPESQ

O

OCH3OH

OH

O

CH (CH2)6

CH2

HC OH

HC

CH2

(CH2)6 CH3

COOH

CH3

O

CH3OH

OH OH

Rooney, A.P., Price, N.P., Ray, K.J., Kuo, T. 2009.Isolation and Characterization of Rhamnolipid-Producing Bacterial Strains from a BiodieselFacility. FEMS Microbiological Letters. 295:82-87.

Biodiesel stability

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CEPESQ

Carotenoids

CH3CH3

CH3

CH3CH3CH3

R2

HO

R1

O

Tocopherols

TocotrienolsCH3

CH3

CH3

CH3CH3CH3

R2

HO

R1

O

Biodiesel stability

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Sample Oxidation stability (h)

B100 at 110oC 6.3

B100 + b-Carotene (50 ppm) at 110oC 6.1

B100 + b-Carotene (1000 ppm) at 110oC 2.4

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CEPESQ

C C

H H

(CH2)4 CH2H3C

C C

(CH2)7

H H

C

O

O CH3

Diels-Alder

Polymerization

(Carbon deposits in the injection nozzle)

D

Pressure / D

PAHs

(Cancer)

Biodiesel stability

23

http://upload.wikimedia.org/wikipedia/commons/4/45/Rea%C3%A7%C3%A3o_de_Diels-Alder1.gif

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CEPESQ

Used frying oil

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Pros and cons:

o Favorable environmental impact

o Cheap if treated as a residue

o Subject for a number of studies

o Very little contribution to the national

biodiesel matrix

o Complicated and rather costly logistics

o Very unstable and incredibly

heterogeneous, running from premium to

extremely poor biodiesel sources

o Often poorly characterized

o Not often available for biofuels

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CEPESQ

10 12 14 16 18 20 22 24 26 28 30

0

20

40

60

80

100

120

140

160

180

987

6

5

4

3

2

Inte

nsid

ade (

mV

)

tR

(min)

1

Methyl esters tR Cn:m Used frying oil Soybean oil

1 Palmitate 11.83 C16:0 11.11 ±0.06 10.55 ±0.022 Stearate 15.51 C18:0 3.81 ±0.01 4.80 ±0.013 Oleate 15.87 C18:1 25.23 ±0.08 28.56 ±0.04

4 Linoleate16.70 C18:2 cis 49.37 ±0.2 45.86 ±0.03

16.77 C18:2 trans 0.21 ± 0.001 0.885 Linolenate 17.87 C18:3 0.35 ±0.001 3.33 ±0.017 Aracquidonate 19.40 C20:0 0.20 ±0.001 0.228 Behenate 22.42 C22:0 0.47 ±0.006 0.549 Tricosenoate 24.05 C23:0 0.51 0.21

GC-FIDInte

nsi

ty (m

V)

Used frying oil

o Changes in the fatty acid

profile are attributed to the

presence of animal fat and

to the chemical modification

of PUFAs (polyunsaturated

fatty acids)

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CEPESQ

Used frying oil

Hydroperoxides and other

by-products

Volatiles

Hydrocarbons, alde

hydes, ketones, fura

ns, carboxilic

acids, etc.

Non-volatiles

Cyclic

monomers, epoxides, dím

ers, trimers and high

molecular mass

compounds

O2 Oxidation

O

O

O

O

O

O

H2O

Hydrolysis

Fatty acid

OH

O

Triacylglyceride

26

Luiz Ramos



CEPESQ

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H

H

O

OH

O2

OH O

2.OOH

O

OH

3.

Route A -

Route B -

OH

H

O

OH

O

C O

OH

OOH

.

OH

O

OO

H

O

OH

I. Presence of oxygen

OH O

1.

OOH

O

OH

Decomposition of hydroperoxide

Homolytic decomposition

Induced oxidation

O

OH

O

OH

Used frying oil

1. Reactions in the presence of oxygen

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Used frying oil

II. Absence of oxygen

O

OH

1.O

OH

2.O

OH

O

OH

O

OH

O

OHDiels-Alder reaction

2. Reactions in the absence of oxygen

Luiz Ramos



CEPESQ

Parameter Refined soybean oil Used frying oil

Iodine number (mg I2/g) 130.76 ± 1.22 117.75 ± 1.48

Peroxide index (meq/kg) 1.95 ± 0.08 37.08 ± 0.05

Viscosity (mm2/s) 32.48 ± 0.10 44.63 ± 0.08

Acid number (mg KOH/g oil) 0.010 ± 0.001 0.83 ± 0.01

Water (ppm) 157.54 ± 10.22 1080.4 ± 10.48

Specific gravity (kg/m3) 921.14 ± 0.53 922.12 ± 0.42

Average molar mass (g/mol) 873.24 924.21

Coloration Yellow Orange to ochre

Foam Absent Present

Used frying oil

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CEPESQ

Element Quantification limit Results (mg/kg )

K 0.83 1.90 ± 0.13

Mg 0.08 0.30 ± 0.01

Na 0.11 3.60 ± 0.12

P 6.97 7.90 ± 0.18

Used frying oil

30

Used frying oils may elements and/or components that may

compromise biodiesel quality and performance;

Several groups have developed methods to adjust the properties

of used frying oils for biodiesel production

New conversion technologies have also been developed using

homogeneous and/or heterogeneous catalysts

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10 12 14 16 18 20 22

-2

0

2

4

6

8

10

2

Sin

al d

o d

ete

cto

r (R

ID)

tR (min)

1

tRi t

Rf

Mm

Used frying oil

Gel permeation chromatography

31

TAGs

Det

ecto

r re

spo

nse

(R

ID)

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CEPESQ

Used frying oil

1700 1750 1800 1850 1900 1950 2000

1987,8

1757,6

1921,1

1903,7

1890,41873,8

1841,3

1819,8

1802,1

1778,6

1757,6

1746,5

1729,3

1710,1

Inte

nsid

ade r

ela

tiva

m/z

(B)

880 900 920 940 960

969,3

965,3

957,3

953,7

936,8

929,3

923,3

917,7

913,7

907,3

901,7

892,1

885,3

881,3

877,7

Inte

nsid

ad

e r

ela

tiva

m/z

873,2

(A)

Direct infusion in a Varian 320 MS detector

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CEPESQ

Used frying oil

33

O

OH

O

O

O

O

O O

O

O

O

O

O

O

OH

OH

2

3

1

1. Hydroperoxide

2.Ether

3.Cyclohexene

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Biodiesel has evolved a lot in Brazil from its late (re)start in

January 2005

Brazil, USA and Germany are the leading countries in the

release of high level research publications in this field

In the search for alternative routes, much has already been

done in the characterization of non-conventional feedstocks

Oil components such as free sterols and sterol glucosides

may compromise the quality of on-spec biofuels

Usually, well-known procedures such as adsorption and

water washing are enough to adjust the adverse properties

of some non-conventional feedstocks

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Many unconformities attributed to biodiesel production and

use are due to improper storage and handling

By diversifying the feedstocks, one may envisage the need

for additional “cleaning” steps in already well established

production technologies

The current Brazilian standard is second to none with

regard to its limits and quality criteria

With B7, Brazil will soon become the second largest

biodiesel producer in the world

Biodiesel will remain an important component of the World

Energy Matrix for years to come

http://www.biodiesel.gov.br/index_arquivos/index_centro.htm

Thank [email protected]

[email protected]

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