Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
4th
CEPESQ
Química - UFPR
Characterization of minor components in
biodiesel from non-conventional sources
Luiz Pereira Ramos
Chemistry, Federal University of Paraná (UFPR)
www.quimica.ufpr.br/cepesq, [email protected]
Nelson Roberto Antoniosi Filho
Chemistry, Federal University of Goiás (UFG)
[email protected], http://lames.quimica.ufg.br
CEPESQ
Química - UFPR
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
4th
CEPESQ
Química - UFPR
2
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
4th
CEPESQ
Química - UFPR
 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
3
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
4th
CEPESQ
Química - UFPR
ANP Authorized Annual Production Capacity
Monthly compulsory demand for biodiesel
Monthly biodiesel production
4
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
4th
CEPESQ
Química - UFPR
Soybeans
Beff tallow
Cottonseed
73.72
20.29
Chicken fat
Lard (pig fat)
Used frying oil
4.04
0.46
Other materials
0.01
0.47
1.01
5
PROPERTY
METHOD
UNIT
LIMIT
-
LII
Specific gravity at 20 °C
kg/m³
850 a 900
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
°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
h
8
-
EN 14112, EN 15751
Aspect
Flash point, min.
Oxidation stability at 110 °C, min.
ABNT
NBR Luiz Ramos
th
EN/ISO
CEPESQ
4 CISB Annual Meeting
- Química - UFPR
São -Paulo, SP – Nov 2014
7148, 14065
EN ISO 3675 & 12185
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
4th
Poor cold flow properties
CEPESQ
Química - UFPR
Poor oxidative stability
7
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
4th
CEPESQ
Química - UFPR
8
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
4th
CEPESQ
Química - UFPR
 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
9
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
CEPESQ
4th
CH2OH
Química - UFPR
OH
O
O
OH
HN
OH
O
Cholesterol
R
OH
HO
O
Cerebrosides
H2C O C
O
C O C H
R2
H2C O
Phospholipids
R1
O
P O X
O
-
O
H3C(CH2)12CH CH
OH
HO
β-Sitosterol
CH
NH
CH2OPOCH2CH2N(CH3)3
O
COR
R is a fatty acid
Sphingolipids
10
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
4th
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
CEPESQ
Química - UFPR
Free sterols
Esterified sterols
Sterol glycosides
Acylated sterol glycosides
11
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
4th
CEPESQ
Química - UFPR
catalyst
Sterol glycosides
12
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
4th
CEPESQ
Química - UFPR
GC-FID of free steroids present in commercial biodiesel and soybean biodiesel
Bezerra and Antoniosi Filho, Fuel 130 (2014) 149–153
13
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
4th
Unrefined soybean oil
CEPESQ
Química - UFPR
Refined soybean oil
Campesterol (A)
Stigmasterol (B)
β-Sitosterol (C)
Biodiesel from unrefined soybean oil
Biodiesel from refined soybean oil
14
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
4th
CEPESQ
Química - UFPR
GC-FID of free steroids present in commercial biodiesel and soybean biodiesel
Bezerra and Antoniosi Filho, Fuel 130 (2014) 149–153
15
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
CEPESQ
4th
CORN
Química - UFPR
CASTOR
PALM
CRAMBE
BABASSU
PALMISTE
BEEF TALLOW
CHICKEN FAT
SOYBEANS
SUNFLOWER
PEANUT
RAPE
COTTON
MORINGA
oils and fats
biodiesel
16
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
4th
CEPESQ
Química - UFPR
GC-FID Analysis of Free Sterols
Refined soybean oil
Crude soybean oil
17
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
4th
CEPESQ
Química - UFPR
Sterol Glucoside Content in Vegetable
Oils as a Risk for the Production of
Biodiesel – Study of the Technological
Chain Impact – OVDI-ASA
18
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
4th
GC-FID analysis of free
sterols before and after
adsorption and filtration
CEPESQ
Química - UFPR
Untreated biodiesel
Biodiesel treated with
acid-activated Bauxite
19
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
CEPESQ
4th
Biodiesel stability
H
H H
C
H3C
C
H
C C
(CH2)4
Química - UFPR
CH2
O
(CH2)7
C
O CH3
Microbes / Water
H
H H
C
H3C
(CH2)4
C
C C
CH2
Oxidation
H
O
(CH2)7
C
OH
O
C
H3C
(CH2)4
HO
C
OH
C C
CH2
O
(CH2)7
C
O CH3
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
4th
Biodiesel stability
CEPESQ
Química - UFPR
O
CH3
OH
O CH
(CH2)6 CH3
CH2
HC OH
HC
CH3
CH2
OH
O
OH
(CH2)6
O
COOH
CH3
OH
OH
Rooney, A.P., Price, N.P., Ray, K.J., Kuo, T. 2009.
Isolation and Characterization of RhamnolipidProducing Bacterial Strains from a Biodiesel
Facility. FEMS Microbiological Letters. 295:82-87.
21
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
4th
Biodiesel stability
HO
CH3
O
CH3
CH3
CH3
Sample
CH3 stability (h)
Oxidation
CH3
B100
at 110oC
6.3
o
B100
R1 + b-Carotene (50 ppm) at 110 C
HO
6.1
Tocopherols
B100 + b-Carotene (1000 ppm) at 110oC
CH3
R2
O
CH3
Química - UFPR
Carotenoids
R1
R2
CEPESQ
CH3
2.4
CH3
CH3
CH3
Tocotrienols
22
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
CEPESQ
4th
Biodiesel stability
H
D
H H
C
H3C
C
(CH2)4
Química - UFPR
H
C C
CH2
O
(CH2)7
C
O CH3
Pressure / D
Diels-Alder
PAHs
(Cancer)
Polymerization
(Carbon deposits in the injection nozzle)
23
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
4th
Used frying oil
CEPESQ
Química - UFPR
Pros and cons:
o
o
o
o
o
o
o
o
Favorable environmental impact
Cheap if treated as a residue
Subject for a number of studies
Very little contribution to the national
biodiesel matrix
Complicated and rather costly logistics
Very unstable and incredibly
heterogeneous, running from premium to
extremely poor biodiesel sources
Often poorly characterized
Not often available for biofuels
24
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
CEPESQ
4th
Used frying oil
Química - UFPR
180
5
160
140
120
(mV)
Intensidade
Intensity (mV)
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)
100
3
80
60
GC-FID
1
40
20
6
2
4
8
7
9
0
10
12
14
16
18
20
22
24
26
28
tR (min)
Methyl esters
1 Palmitate
2 Stearate
3 Oleate
4
5
Linoleate
Linolenate
7 Aracquidonate
8 Behenate
9 Tricosenoate
tR
Cn:m
Used frying oil
Soybean oil
11.83
15.51
15.87
16.70
16.77
17.87
19.40
22.42
24.05
C16:0
C18:0
C18:1
C18:2 cis
C18:2 trans
C18:3
C20:0
C22:0
C23:0
11.11 ±0.06
3.81 ±0.01
25.23 ±0.08
49.37 ±0.2
0.21 ± 0.001
0.35 ±0.001
0.20 ±0.001
0.47 ±0.006
0.51
10.55 ±0.02
4.80 ±0.01
28.56 ±0.04
45.86 ±0.03
0.88
3.33 ±0.01
0.22
0.54
0.21
30
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
CEPESQ
4th
Used frying oil
Cyclic
monomers, epoxides, dím
ers, trimers and high
molecular mass
compounds
Hydrocarbons, alde
hydes, ketones, fura
ns, carboxilic
acids, etc.
Non-volatiles
Volatiles
Fatty acid
O
Química - UFPR
Hydroperoxides and other
by-products
H2 O
OH
O
Hydrolysis
O2 Oxidation
O
O
O
O
Triacylglyceride
O
26
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
CEPESQ
4th
Used frying oil
Química - UFPR
I. Presence of oxygen
1. Reactions in the presence of oxygen
OH
H
1.
HO
O
O
H
HO O
O2
HO
2.
OH
OOH
HO O
O
O
Route A -Homolytic decomposition
3. Decomposition of hydroperoxide
OOH
O
HO
OH
O
O
O
H
O
OH
O
OOH
C.
H
OH
O
OH
Route B - Induced oxidation
O
HO
27
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
4th
Used frying oil
CEPESQ
Química - UFPR
Absence of oxygen
2.II. Reactions
in the absence of oxygen
O
1.
O
OH
OH
OH
2. Diels-Alder reaction
O
O
OH
O
OH
OH
O
28
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
4th
Used frying oil
CEPESQ
Química - UFPR
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
29
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
4th
Used frying oil
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
Química - UFPR
 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
30
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
4th
Used frying oil
CEPESQ
Química - UFPR
10
TAGs
(RID)
Detector
detector (RID)
Sinal doresponse
8
6
4
2
Mm
2
1
tRi
0
tRf
Gel permeation chromatography
-2
10
12
14
16
18
20
22
tR (min)
31
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
CEPESQ
4th
Used frying oil
(A)
1746,5
(B)
901,7
881,3
Química - UFPR
1802,1
1903,7
1757,6
936,8
907,3
969,3
Intensidade relativa
917,7
923,3
885,3
873,2
957,3
913,7
892,1
1757,6
929,3
965,3
953,7
1819,8
Intensidade relativa
877,7
1778,6
1873,8 1890,4
1729,3
1710,1
1987,8
1841,3
1921,1
880
900
920
m/z
940
960
1700
1750
1800
1850
1900
1950
2000
m/z
Direct infusion in a Varian 320 MS detector
32
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
CEPESQ
4th
Used frying oil
1
Química - UFPR
OH
O
OH
O
O
O
O
O
O
2
O
O
3
1. Hydroperoxide
2.Ether
O
O
HO
O
3.Cyclohexene
O
33
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
4th
CEPESQ
Química - UFPR
 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
34
Luiz Ramos
CISB Annual Meeting
São Paulo, SP – Nov 2014
4th
CEPESQ
Química - UFPR
 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
35
Thank you!
[email protected]
[email protected]