Professional Documents
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4/10/07
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Page 1
biofuels
2008
Supplement to PTQ
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99090_Bioethanol_e_A4.indd 1
biofuels
plant & technology
Editor
Rene G. Gonzalez
editor@petroleumtechnology.com
Graphics Editor
Mohammed Samiuddin
graphics@petroleumtechnology.com
Editorial
PO Box 11283
Spring TX 77391, USA
tel +1 281 374 8240
fax +1 281 257 0582
Advertising Sales Manager
Paul Mason
sales@petroleumtechnology.com
Advertising Sales
Bob Aldridge
sales@petroleumtechnology.com
Perkin Elmer
Publisher
Nic Allen
publisher@petroleumtechnology.com
Circulation
Jacki Watts
circulation@petroleumtechnology.com
Cover: The BP Rotterdam refinerys (BPRR) ETBE unit revamped, with only minor
changes to existing equipment, to produce ETBE based on etherification of
isobutylene and bio-ethanol. BPRR is the first refinery in The Netherlands to produce
biofuels with this revamped unit.
Photo courtesy of BP and CDTech
2007. The entire content of this publication is protected by copyright full details of which are available from the publishers. All
rights reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any
means electronic, mechanical, photocopying, recording or otherwise without the prior permission of the copyright owner.
The opinions and views expressed by the authors in this publication are not necessarily those of the editor or publisher and while
every care has been taken in the preparation of all material included in Petroleum Technology Quarterly the publisher cannot be held
responsible for any statements, opinions or views or for any inaccuracies.
Ins_873Biodiesel_Ranci_A4e
Biodiesel with
quality guarantee
Reliable determination
of the oxidation stability
873 Biodiesel Rancimat unparalleled accuracy
High quality heating block, sensors and measuring electronics
guarantee outstanding precision
873 Biodiesel Rancimat simple operation
Robust, easy-to-handle accessories
Easy sample introduction
Simple and quick measuring setup
Ecknauer+Schoch ASW
I o n
a n a l y s i s
Metrohm Ltd.
CH-9101 Herisau/Switzerland
Phone +41 71 353 85 85
Fax +41 71 353 89 01
www.metrohm.com
info@metrohm.com
Automation
www.eptq.com
Economic comparison of various first- and secondgeneration biofuels process routes, including catalytic
pyrolysis of biomass
$/Boe
Crude Oil
$/GJ
60
10
Ethanol
Sugarcane (Energy = biowaste)
Sugarcane (Energy = fossil)
Cellulose
54
90
120
9
15
20
Diesel
Biodiesel from Jatropha
BTL via GTL
156
110
26
18
72
60
12
10
Table 1
As the content of biofuels within gasoline and diesel is on the
rise, manufacturers of analytical instrumentation are striving
to meet the standards for analysing biofuels. Biofuels used for
combustion engines are biodiesel and bioethanol. The
following discussion lists some of the instruments amenable
to ensure regulatory specifications and new standards
evolving around the new applications.
Biodiesel
ASTM D6751-07a is the standard specification for biodiesel
fuel blendstock (B100) for middle distillate fuels in the USA.
The Grabner Instruments IROX-Diesel can determine the
concentration of biodiesel according to D6751-07a in diesel
fuel from 0 to 40 volume per cent (0-40 vol%) using FT-IR
spectroscopy. The measurement method is under evaluation
within the ASTM committee and will become a standard
method within the year 2008 (new standard test method for
determination of biodiesel [fatty acid methyl esters: FAME] in
diesel fuel oil using mid-infrared spectroscopy). The actual
draft is available within the ASTM (WK10753).
In addition to the determination of total biodiesel, the
IROX uses a math model to separate overlapping peaks for
deriving the content of FAME, FAEE and even higher alcohol
esters within the biodiesel fuel blend.
While the vapour pressure of biodiesel blends is not
significantly influenced, even by small amounts of free
alcohols, the flash point of biodiesel drops dramatically from
120C down to 60C with only some tenth of weight per cent
(0.10 wt%) of free methanol. With a new standard method
currently worked on for available instruments, the flash
point of pure biodiesel can be controlled.
Distillation is a common quality check for fuel distillates.
Biofuels 2008 3
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4 Biofuels 2008
QKOm`i_ja@oc\ijgdiB\njgdi`#?1.23$
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www.eptq.com
www.eptq.com
Biofuels 2008 5
www.eptq.com
Biofuels 2008 7
GBF-30-07 PTQ Ad
6/7/07
1:58 PM
Page 1
Make biofuels
better with Grace
Ethanol Drying
Biodiesel Purification
Biodiesel Analysis
www.GraceBiofuels.com
Biofuels@Grace.com
GRACE is a trademark, registered in the United States and/or other countries, of W. R. Grace & Co.-Conn.
2007 W. R. Grace & Co.-Conn. All Rights Reserved.
www.eptq.com
Challenges
Biofuels 2008 9
10 Biofuels 2008
Opportunities
www.eptq.com
Solved by Nature
SD-CHEMIE AG
Lenbachplatz 6
80333 Munich, Germany
Phone: +49 89 5110-306
Fax: +49 89 5110-405
Ralf.Weishaupt@sud-chemie.com
www.sud-chemie.com
12 Biofuels 2008
www.eptq.com
www.eptq.com
Biofuels 2008 13
Sulfur Monitors
and Analyzers
Determination of Sulfur
in fuel and oils on-line, at-line
and in the laboratory
Catalytic conversion of
cellulosic biomass
Future process routes based on heterogeneous catalysis will enable effective and
economical conversion of solid biomass into sustainable fuels, chemicals and energy.
This conversion is based on the effective opening or unlocking of solid biomass
Paul OConnor and Rob van der Meij
BIOeCON BV
www.eptq.com
TW yr
178000
120000
53000
16000
EJ
5500000
128
46
4000
1426
14
430
600-1800
100-350
3700000
Table 1
Biofuels 2008 15
Energy
capture
Energy
storage
Energy
distribution
Power
train
Via
fossil fuels
Refinery
hydrocarbon
fuels
gas
stations
ICE
(+HEV)
Refinery
biofuels
gas
stations
ICE
(+HEV)
Via
biomass
ICE =
HEV =
FC =
EV =
Existing
Modified
New
Energy stored in
biomass represents 3x
todays global
energy demand
Biomass is readily
available all over
the world
Use of renewable
biomass resources
will limit increase of
greenhouse gas (CO2)
emissions
16 Biofuels 2008
www.eptq.com
Lignin
Cellulose
Cellulose
chain
Shorter
cellulose
chain
Hemicellulose
Figure 3 Unlocking the cellulose from the woody structure enables the conversion
A more simple and robust (in terms
of feedstock flexibility) approach is to
convert the solid biomass into a liquid
(BTL) by direct liquefaction. Several
thermal and thermo-catalytic processes
are under development in this area. A
drawback is that the quality of the biooil produced is often rather poor, and
extensive treatment and upgrading is
required in order to produce the right
components for transportation fuels
and/or chemicals.
An interesting new approach in this
respect is catalytic pyrolysis of biomass,
whereby catalytic technology is used to
achieve the liquefaction of the solid
biomass under milder conditions and
at a lower cost. The technology is
similar to FCC (fluid catalytic cracking)
and therefore requires less time to
www.eptq.com
Biofuels 2008 17
Solid
Charcoal, briquettes
Gas-to-liquids (GTL)
Gasification
Synthesis gas
OH
HO
HO
OH
Chemical
OH
Sollubilise
Liquefaction
Bio-oils, acids
Thermo-chemical
Pyrolysis, FCC
Applying catalysis to
break the fibrous cellulosic
structures
18 Biofuels 2008
Biomass conversion
technologies
Oil feed
Biomass feed
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Biofuels 2008 19
Quality control
of biofuels
For quality control of biofuels, determination of oxidation stability, iodine and acid
number as well as water, alkali metal and alkaline earth metal content are important.
Titrimetric and ion chromatographic analyses are also addressed
A. Steinbach, U. Loyall, B. Zumbrgel, C. Haider, G. Spinnler, R. Schlink and A. Wille
Metrohm AG
www.eptq.com
While the
standardisation of
biodiesel in Europe has
been well established by
the EN 14214 since 2003,
the European standard
for bioethanol, the prEN
15376 is currently under
approval
biodiesel phase is separated from the
more dense glycerin phase by
gravitational settling or centrifugation.
Subsequently, the methyl esters, which
still contain large amounts of residual
alcohol, traces of dispersed glycerin and
unreacted sodium hydroxide or soaps,
are cleaned by a water-wash. Remaining
water and poorly water-soluble
impurities, such as unreacted feedstock
or the mono- and di-glycerides, are
removed by further steps such as
distillation or stripping.
In 1908, some years after the
development of the diesel engine,
Henry Ford designed the Ford Model-T
to run on ethanol. However, the low
petroleum prices and the seemingly
inexhaustible fossil fuel reserves also
displaced ethanol. Not until the
worldwide oil crisis in 1973 did Brazil
and the USA launch their first ethanol
programmes, paving the way for their
leadership position in the production
and utilisation of bioethanol.
H2C
COO
R1
HC
COO
H2C
COO
R*
COO
R1
H2C
OH
R2 + 3R*OH
R*
COO
R2 + HC
OH
R3
R*
COO
R3
OH
NaOH
Triglyceride
Alcohol
Fatty acid
alkyl esters
H 2C
Glycerine
Biofuels 2008 21
EN 14214/14213
Property
EN 14214
Test method
Oxidative stability
[h]
Iodine value
[g I2/100 g]
Acid number
[mg KOH/g]
Water content
[mg/kg]
Group I metals (Na + K)
[mg/kg]
Group II metals (Ca + Mg)
[mg/kg]
Total glycerin
[% mass]
EN 14213
ASTM D 6751
Limits
Test method
EN 14112
> 6
> 4
EN 14111
< 120
< 130
EN 14104
Limits
EN 14112
>3
< 0.5
ASTM D 664
< 0.5
< 500
EN ISO 12937
EN 14108
EN 14109
ASTM D 2709
< 500
< 5.0
EN 14538
< 5.0
EN 14538
< 5.0
EN 14538
< 5.0
EN 14105
< 0.25
ASTM D 6584
< 0.24
Table 1a
Temperature dependence of the
induction time (mean of two
determinations)
Temperature
[C]
120
110
100
Induction time
[h]
3.3
6.3
11.6
Table 2
standard EN 14213 defining the
minimal requirements for biodiesel
used as heating oil or as a blending
component for heating oil.
Structure indices/quality
indices
22 Biofuels 2008
ASTM D 4806
ASTM D 5798
prEN 15376
Test method
Limits
Test method
Limits
ASTM D 1613
< 0.007
< 0.005
prEN 15491
< 0.007
ASTM E 1064coul
ASTM E 203vol
< 1 [v/v]
prEN 15489
< 0.3%
< 40
< 1
prEN 15484
prEN 15492
< 20
ASTM D 512
Inorganic sulphate
[mg/L]
ASTM D 7318pot
ASTM D 7319IC
< 4
pH
Copper content
[mg/kg]
ASTM D 6423
ASTM
D 1688
6.5 - 9.0
prEN 15490
6.5 - 9.0
< 0.10
< 0.07
prEN 15488
< 0.1
Table 1b
the US and Brazil dispose of two
well-established standards, the ASTM D
4806 and the ASTM D 5798 for
denatured fuel ethanol only and for
mixtures of bioethanol and gasoline
(Ed75-Ed85), respectively (Table 1b).
In view of the fact that the quality
control of biodiesel begins with the
refining of the vegetable oil feed, this
discussion stresses the importance of
feedstock acid number and water
content. However, emphasis is on
specifications and test methods
prescribed by the two biodiesel
Oxidation stability of
biodiesel
www.eptq.com
200
Conductivity, S/cm
175
Air inlet
150
125
Measuring
cell
100
75
50
25
0
Reaction vessel
0
4
5
Time, hr
Conductivity
cell
www.eptq.com
Absorption
solution
(water)
Oil sample
Heating block
(110C)
Blank
Biodiesel
Number of determinations n
Mean value thiosulphate consumption [ml]
Iodine number [g iodine/100g sample]
Standard deviation
Relative standard deviation [%]
3
47.71
7
33.79
114.40
0.50
0.44
Table 3
Biofuels 2008 23
200
175
Conductivity, S/cm
150
125
100
75
50
120C
110C
100C
25
0
0.0
2.5
5.0
7.5
Time, hr
10.6
12.5
15.0
Figure 3 Plots of conductivity (S/cm) versus time (h) obtained at 100, 110 and
120C
unrefined vegetable oils containing
natural antioxidants. During refining,
these antioxidants get partly lost and
oxidation stability decreases. However,
premature degradation can be overcome
by the addition of synthetic
antioxidants. Their effectiveness can
accurately be investigated with the socalled Rancimat method.
The Rancimat method mimics
oxidation of a biodiesel sample at a
fixed temperature, usually far above
ambient. The result is then extrapolated
to the stability under real-world
conditions. In practice, a stream of
purified air is passed through the heated
sample (usually 110C) and is
subsequently bubbled through a vessel
containing deionised water (Figure 2).
Titer
3
0.987
0.34%
Acid number
9
0.202 mg/g
0.94%
Table 4
Water content
Minimum
value xmin
Coulomat AG (without solubiliser)
Coulomat AG + Xylene
Coulomat AG Oil (CHCl3 + Xylene)
Coulomat A (CHCl3)
Coulomat AG-H (long-chain alcohol)
1
184.9
192.8
179.4
188.9
186.1
Maximum
Mean
RSD
value xmax
value x1
[ppm]
[%]
189.6
199.5
183.0
194.3
191.5
187.7
196.6
181.3
191.7
189.1
0.8
1.1
0.7
1.0
0.9
Difference
Repeatability
xmax-xmin
r 100
[ppm]
4.7
6.7
3.6
5.4
5.4
25.7
26.3
25.2
25.9
25.8
Mean of 10 determinations
Table 5
24 Biofuels 2008
www.eptq.com
410
Biodiesel sample
Blank titration
160
140
120
EP1
U, mv
DET U
100
EP1
80
60
40
20
0
10
20
50
60
Water determination in
biodiesel and ethanol
1 mg sulphate/kg EtOH
5 mg sulphate/kg EtOH
10 mg sulphate/kg EtOH
20 mg sulphate/kg EtOH
430
450
Blank
1 mg sulphate/kg EtOH
5 mg sulphate/kg EtOH
10 mg sulphate/kg EtOH
20 mg sulphate/kg EtOH
10
30
470
40
Figure 4 Titration curves for liberated iodine, titrated with sodium thiosulphate
solution
MET U
30
Volume, ml
EP1
490
50
EP1
EP1
530
U, mv
U, mv
510
EP1
550
EP1
70
EP1
570
EP1
90
EP1
590
EP1
610
110
630
650
130
5
6
Volume, ml
10
5
6
Volume, ml
10
Figure 5a & b Titration curves of sulphate determinations in ethanol with a lead nitrate solution
www.eptq.com
Biofuels 2008 25
140
Conductivity, S/cm
120
100
Chloride
(2.5 mg/L)
80
r=0.01874x
where (x) is the mean value of all
test results given as a mass fraction
in per cent rounded off to 0.001%.
60
40
Sulfate
(1 mg/L)
20
6
7
8
Time, min
10
11
12
13
14
Experimental
Between 0.9 and 3.0g biodiesel sample
is directly injected into the reaction
solution with a syringe. Once all the
available water has reacted (equivalence
point), the indicator electrode detects
the first excess of iodine and the KFT
stops. The amount of water is calculated
by measuring the electric charge needed
for iodine generation.
Irrespective of the KF reagent used,
all results are in the same ppm range
(Table 5). The differences (xmax-xmin) are
much smaller than the repeatabilities
(r) defined by EN ISO 12937. This
clearly shows that direct KFT provides a
far better repeatability than is required
by EN ISO 12937. The same applies for
the automated pipetting system of
Metrohm, which has been especially
developed
for
high
sample
throughputs8.
Accordingly, for ethanol the ASTM
standard E 1064 in ASTM D 4806
prescribes the coulometric KFT of low
water contents. For water contents
greater than 2%, the recommended test
method is volumetric titration as per
ASTM E 203 in ASTM D 4806.
[ppm]
SO42 conc.
[ppm]
RSDa
[%]
nb
Recovery rate
[%]
SO42 conc.
[ppm]
RSDa
[%]
nb
Recovery rate
[%]
0.998
4.989
9.978
19.965
0.978
5.229
10.047
21.627
0.81
0.41
0.52
1.08
3
4
4
5
98
104.8
100.7
108.3
1.063
5.268
10.063
21.735
1.46
0.23
0.24
0.75
3
3
3
4
106.5
105.6
100.9
108.9
Table 6
26 Biofuels 2008
www.eptq.com
2.8
Column:
Eluent:
Flow:
Sample volume:
Conductivity, S/cm
2.4
2.0
Metrosep C2 150
2 mmol/L HNO3 + 11% acetone
1.0 mL/min
20 L
Calcium
(5.0 mg/L)
1.6
1.2
0.8
Potassium
Sodium (1.2 mg/L)
(0.1 mg/L)
0.4
0.0
Magnesium
(0.7 mg/L)
8
10
Time, min
12
14
16
18
Figure 7 Separation and detection of alkali metals and alkaline earth metals
a) Titration
As an example for potentiometric
biofuel titrations, the determination of
sulphate in ethanol according to ASTM
D 7318 is presented. The determination
of chloride, which can be carried out by
mercurimetric or argentometric titration
or with a Cl-selective electrode, is
beyond the scope of this article.
A 100g bioethanol sample is spiked
with known amounts of a sulphate
standard. After the addition of 1.0mL
0.1 mol/l perchloric acid, the sulphate
is precipitated with a lead nitrate
solution. The Pb-selective electrode
detects the first excess of lead ions at
the equivalence point. A double
junction Ag/AgCl (Figure 5a) or a glassycarbon rod electrode (Figure 5b) are
used as reference electrode.
While sulphate concentrations
between 5 and 10ppm result in recovery
rates of 100.7105.6%, sulphate
contents of 1 and 20ppm provide
recovery rates of 98.0106.5% and
108.3108.9%, respectively (Table 6).
Correlation coefficients of real
concentrations versus determined
concentrations for the double junction
Ag/AgCl and the glassy carbon rod
28 Biofuels 2008
and
0.9991,
b) Ion chromatography
After direct injection, chloride and
sulphate are separated on an anion
exchange column and then determined
quantitatively
by
suppressed
conductivity detection.
The limits of detection for chloride
and sulphate are 0.6 and 0.2ppm,
respectively. Even after 1500 ethanol
injections containing denaturants and
hydrogen peroxide, the analytical unit
still provides stable retention times,
repeatable peak areas and consistent
concentration values9. This highlights
the extraordinary ruggedness of the
applied micro packed tri-chamber
Antioxidants in biodiesel
90
Column:
Column temperature:
Eluent:
Porontosil 1205C18H
35C
90% acetonitrile + 10%
dichloromethane
1.0 mL/min
Flow:
UV detector cell wavelength: 220 nm
Sample volume:
10 L
80
70
Conductivity, S/cm
Experimental
The samples are extracted with dilute
nitric acid, dialysed and then injected
directly into the IC system. The complete
sample preparation procedure and
analysis takes place fully automatically.
The setup consists of the proprietary
861 Advanced Compact IC with
Metrohm inline extraction and
dialysis.
60
50
40
Baynox
(50 mg/L)
30
20
-Tocopherol
(5 mg/L)
10
0
10
12
Time, min
14
16
18
20
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Experimental
Because of their structural similarities, vitamin E (-tocopherol
and Baynox can be determined together in a single analysis
(Figure 8). To improve solubility, dichloromethane is added
to the eluent and analyte solutions. The biodiesel samples
should be diluted 1:1000. The analytes are separated at 35C
and then determined quantitatively using UV detection.
Implications
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6/'%,"53#( \ THE BIOPROCESS COMPANY
4HE PREMIER SUPPLIER OF
02/#%33 %.').%%2).'