Accurate Determination of Ether/Alcohol Octane

Synergies in Specific Base Fuel Matrices

Jacques van Heerden; Petrus N. J. Roets;
Johan J. Botha; Heinrich F. Strauss
ISAF XV
International Symposia on Alcohol Fuels
September 26 28, 2005
Overview
~ Background
~ Objectives
~ Methodology
~ Results
~ Conclusions
Background - Pressures on refiners
~ Vehicle manufacturers are
demanding higher octane
unleaded gasoline
~ Use of oxygenates is an
alternative to reduce carbon
monoxide emissions
~ J anuary 2006 total Pb phase
out in SA oxygenates to
cater for octane deficit
Background - Sasols Experience with Oxygenates
~ Experience with alcohol 8-12
vol % in gasoline 1981-2001
~ Experience with alcohol below
2 vol % in gasoline since
2000
~ Experience with TAME since
introduction of unleaded
gasoline in the South African
market in 1996
~ Have previously shown that
there are synergistic effects
when blending alcohol and
ether in same gasoline blend
(ISAF XIV, Thailand, 2002)
Physical and Chemical Properties
Oxygenate Ethanol MtBE TAME
Chemical Formula C
2
H
6
0

CH
3
CH
2
-0H
C
5
H
12
0

CH
3
-O-C(CH
3
)
3

C
6
H
14
0

C
2
H
5
C(CH
3
)
2
-O-CH
3

Chemical Structure



Molecular Weight 46.07 88.15 102.18
Density, kg/l 0.789 0.740 0.764
Composition, weight
%

Carbon 52.2 68.1 70.5
Hydrogen 13.1 13.7 13.8
Oxygen 34.7 18.2 15.7
Boiling
Temperature, C
77-79 54-56 85-87
Research Octane
Number
129 116 112
Motor Octane
Number
96 101 99
Reid Vapour
Pressure, kPa
15.86 53.78 10.34
Flash Point, C
12 -28 -11
Water Solubility
(g/100mL)
Miscible
10
5.1 <0.1???

Background - Ethers vs. Ethanol
~ Maximum allowable: 15 vol. % vs. 10 vol. % -
3.7 mass% O
2
~ Traditionally ethers transported in gasoline via
pipeline ethanol cannot be handled in multi-
product pipelines
~ Ethanol blends are not sent through pipeline
systems because they may pick up water and
other impurities in transit.
~ Sasol has successfully transported alcohol
blended in gasoline via pipeline since 1998
~ Gasoline RVP: MTBE & TAME very similar to
gasoline ethanol increases RVP
~ Refiners must reduce lighter components in
summertime to reduce VOCs
vs
Objectives
~ The objective of this blending study was to verify/quantify the
possible octane benefits of using fuel alcohol (EtOH) and the
ethers (MTBE and TAME) as co-oxygenates in unleaded
gasoline blending.
~ This study comprises the blending octane properties of 95/5
Sasol Fuel Alcohol (SFA) (95% ethanol and 5% propanol)
produced by the Sasol Synfuels facility, and TAME and MTBE
over a concentration range of 3% and 1 10% respectively.
Methodology - Octane Synergies
~ Synthetic and Petroleum derived unleaded gasoline containing 3
volume percentage Sasol Fuel Alcohol (SFA) were used as base fuels
~ Ether (MTBE and TAME) was added, at increasing addition rates by
volume, to determine the effect of the oxygenates on the octane
numbers (RON and MON)
~ As a reference, gasoline blends with no oxygenates were used and the
ethers were added in same ratios as mentioned above
~ Octane ratings of the blends were determined as per ASTM standard
test methods
~ The blending octane of the oxygenates was determined using linear
equations
Results - Blending Research Octane Number
105
110
115
120
125
130
TAME in FT Base MTBE in FT Base TAME in Pet Base MTBE in Pet Base
0 vol% SFA
3 vol% SFA
~The increase of the BRON when SFA is added petroleum based
gasoline is significantly higher if compared with FT based gasoline
Results - Blending Motor Octane Number
94
96
98
100
102
104
106
108
110
TAME in FT Base MTBE in FT Base TAME in Pet Base MTBE in Pet Base
0 vol% SFA
3 vol% SFA
~The addition of SFA reduce the BMON of both TAME and MTBE
for FT base gasoline
Results - RON Gain in F-T Base Gasoline
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
1 % MTBE 3% MTBE 6% MTBE 10% MTBE 1% TAME 3% TAME 6%TAME 10% TAME
Ether Content
w/o SFA With 3-vol% SFA
Base RON = 88.5
Results - RON Gain in Petroleum Base Gasoline
0
1
2
3
4
5
6
7
1 % MTBE 3% MTBE 6% MTBE 10% MTBE 1% TAME 3% TAME 6%TAME 10% TAME
Ether Content
w/o SFA With 3-vol% SFA
Base RON = 90.8
Results Ave Delta in Blending Research Octane Number
0
2
4
6
8
10
12
14
TAME in FT Base MTBE in FT Base TAME in Pet Base MTBE in Pet Base
Results Ave Delta in Blending Motor Octane Number
-6
-5
-4
-3
-2
-1
0
1
2
3
4
TAME in FT Base MTBE in FT Base TAME in CO Base MTBE in CO Base
Discussion
~ The research octane number gain with the addition of ether in
a base gasoline, which contains alcohol, is higher than with a
base gasoline that does not contain any alcohol.
~ The blending octane values of the ethers in the crude oil
based material are higher than the corresponding values in
the Fischer-Tropsch derived material.
~ This may be attributed to differences in olefin content between
the two base fuels without alcohol.
Conclusions
~ The blending octane ethers compares very well with that of
the values given in literature.
~ Even the addition of low concentrations of alcohol to the
unleaded base fuel has a significant effect on the octane
number of the resulting gasoline-oxygenate blend.
~ The gain in octane with the addition of ether is higher with a
base fuel containing alcohol.
~ The composition of the base fuel appear to have significant
effect on the blending octane number of the oxygenates, i.e.
high olefin content affects lower blending octane of
oxygenates and vice versa
Questions?
Background - Properties of commonly used Oxygenates