characterization of minor components in biodiesel from non...
TRANSCRIPT
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
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
CEPESQ
2
Luiz Ramos
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
CEPESQ
3
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
Luiz Ramos
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
CEPESQ
4
ANP Authorized Annual Production Capacity
Monthly compulsory demand for biodiesel
Monthly biodiesel production
Luiz Ramos
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
CEPESQ
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
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
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
Luiz Ramos
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
CEPESQ
Poor cold flow properties Poor oxidative stability
7
Luiz Ramos
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
CEPESQ
8
Luiz Ramos
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
CEPESQ
9
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
Luiz Ramos
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
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-
10
Luiz Ramos
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
CEPESQ
11
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
Luiz Ramos
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
CEPESQ
Sterol glycosides
12
catalyst
Luiz Ramos
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
CEPESQ
Bezerra and Antoniosi Filho, Fuel 130 (2014) 149–153
GC-FID of free steroids present in commercial biodiesel and soybean biodiesel
13
Luiz Ramos
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
CEPESQ
Unrefined soybean oil Refined soybean oil
Campesterol (A)
Stigmasterol (B)
β-Sitosterol (C)
Biodiesel from unrefined soybean oil Biodiesel from refined soybean oil
14
Luiz Ramos
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
CEPESQ
Bezerra and Antoniosi Filho, Fuel 130 (2014) 149–153
GC-FID of free steroids present in commercial biodiesel and soybean biodiesel
15
Luiz Ramos
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
CEPESQ
16
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
Luiz Ramos
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
CEPESQ
17
Crude soybean oil
Refined soybean oil
GC-FID Analysis of Free Sterols
Luiz Ramos
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
CEPESQ
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
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
CEPESQ
19
Untreated biodieselGC-FID analysis of free
sterols before and after
adsorption and filtration
Biodiesel treated with
acid-activated Bauxite
Luiz Ramos
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
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
Luiz Ramos
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
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
21
Luiz Ramos
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
CEPESQ
Carotenoids
CH3CH3
CH3
CH3CH3CH3
R2
HO
R1
O
Tocopherols
TocotrienolsCH3
CH3
CH3
CH3CH3CH3
R2
HO
R1
O
Biodiesel stability
22
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
Luiz Ramos
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
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
Luiz Ramos
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
CEPESQ
Used frying oil
24
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
Luiz Ramos
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
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)
Luiz Ramos
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
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
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
CEPESQ
27
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
Luiz Ramos
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
CEPESQ
28
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
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
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
29
Luiz Ramos
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
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
Luiz Ramos
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
CEPESQ
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)
Luiz Ramos
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
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
32
Luiz Ramos
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
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
Luiz Ramos
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
CEPESQ
34
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
Luiz Ramos
4th CISB Annual Meeting
São Paulo, SP – Nov 2014Química - UFPR
CEPESQ
35
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