BLENDING PROPERTIES OF MTBE AND OTHER OXYGENATES IN GASOLINE

Mohammad Ashraf Ali and Halim Hamid

Center for Refining & Petrochemicals, The Research Institute,
King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia.
INTRODUCTION
Methyl Tertiary Butyl Ether (MTBE) has been accepted worldwide as an octane booster and it is
being blended with gasoline upto 15 volume percent. The demand for MTBE is growing rapidly
and it is the fastest growing chemical nowadays because it has replaced lead alkyl compounds in
gasoline. The use of lead and other metal containing compounds e.g., tetraethyl lead (TEL),
tetramethyl lead (TML) and methylcyclopentadienyl manganese tricarbonyl (MMT) as gasoline
additives for octane boosting is being discouraged. The emission of their combustion products
from the vehicle exhausts creates atmospheric pollution causing serious health hazards. United
States and some European countries have imposed a complete ban on the use of such compounds.
Consequently other blending agents are required to replace the metal based agents presently in use
in order to increase the octane of gasoline. To have lead free high octane gasoline, various
components such as methanol, tertiary butyl alcohol (TBA), secondary butyl alcohol (SBA),
tertiary amyl ethyl ether (TAME) and MTBE can be used. Among these possibilities, MTBE
appears to be the most effective choice because its physical, chemical and thermal properties are
compatible with that of gasoline, especially in the boiling range where gasoline typically show
lowest antiknock characteristics.

MTBE has exhibited highest growth over the past decade among all the oxygenates which are
being blended in gasoline as octane improvers. World capacity of MTBE has increased
approximately over ten-fold in this period and expected to increase further in this decade.
Currently, MTBE has a world capacity of 12 million tons per year with a projection that this figure
will increase to 20 million tons per year by 1994. This increased use of the MTBE is due to the

phasing out of lead from gasoline mandated by the Environmental Protection Agency. EPA has
permitted the addition of MTBE in the gasoline up to 15 volume percent which corresponds to 2.7
percent oxygen. The addition of MTBE not only increases the octane number but also reduces the
toxic exhaust of the vehicles. Contrary to the leaded gasoline, catalytic converters can be used in
the vehicles operating on gasoline containing MTBE.

MTBE is an effective octane booster and volume extender for unleaded gasoline. However, it
should be made clear that MTBE is not as efficient as tetraalkyl lead compounds as far as specific
octane number improvements are concerned. An advantage of its use is that it enables the amount
of gasoline produced from a refinery to be increased for a given crude run, firstly by adding
volume to the gasoline pool and secondly be reducing the severity of the naphtha reforming and
conversion operations. MTBE also allows the low octane components such as straight run
gasoline and raffinates to remain in the pool and reduce the amount of expensive petrochemical
aromatics that would be required to boost octane number.

The addition of MTBE affects the properties of gasoline. The change in properties depends not
only upon the characteristics of the base gasoline but also on the concentration of MTBE. The
behavior of MTBE varies when blended with different gasolines at different concentrations. The
exact amount of MTBE required for a particular lead content reduction or octane number
improvement depends on the properties of the MTBE and the composition of the gasoline base
stock.
PROPERTIES OF MTBE
The physical, chemical and thermal properties of MTBE are given in Table I [1-37]. MTBE is an
excellent high-octane gasoline component and it is combustible, non-oxidizable, clear, colorless
liquid of low viscosity with a distinct odor which is neither pleasant nor nauseating.

Octane Number
The output of an engine is determined by its knocking. Excess of knocking could damage the
engine. Low engine speed knock is usually audible to the driver but is notdamaging to the engine.
High engine speed knock, however, is often inaudible above the engine, road and wind noise. The
most severe knock, which can be very damaging, often occurs at motor way cruising speeds of
4000 to 5000 rpm and modern high compression engines increase the tendency to knock. Many
engines will fail in less than 50 hours under conditions of heavy knock and the damaging effect of
knock is cumulative [38].

The same study also concludes that the maximum engine speed

associated with knock is greatly reduced with MTBE. Laboratory Research and Motor Octane
rating procedures such as ASTM methods D-2699 and D-2700 are not suitable for use with neat
oxygenates such as MTBE.

Octane values obtained by these methods are not useful in

determining knock-limited compression ratios for vehicles operating on neat oxygenates when
blended with gasoline [36].
The octane value of MTBE is measured by its BOV (blending octane value) [39]. This value is
calculated from the difference between the octane value of a base gasoline with a known amount
of MTBE and the base gasoline without MTBE. The formula for BOV calculation is given below:

BOV

ON

ON

(1 x)

base

ON

base

ON

ON
x

base

where
ON

RON or MON of base gasoline MTBE blend

ONbase =

RON or MON of base gasoline

Volume fraction of MTBE

The range of MTBE blending octane numbers is given below [6,13]. This range is determined as a
result of the large amount of experimental data obtained in the formulation of gasolines within the
specification limits.

Blending RON

115 135

Blending MON

98 110

Blending (RON + MON)/2

106.5 122.5

The blending octane numbers of MTBE are very sensitive to the composition and octane numbers
of the unleaded gasoline base [40]. The MTBE blending octane number generally rises under the
following cases: when base gasoline octane number decreases, MTBE concentration in the
gasoline decreases or the saturate content of the gasoline increases.
Addition of MTBE increases the RON and MON of a gasoline. The effect of MTBE on the
antiknock properties of the three types of base gasolines were determined. The RON of the
gasolines were 84.6, 90.5 and 93.7 whereas the MON were 79.0, 83.0 and 84.0 respectively.
MTBE in the concentration levels of 5, 10 and 15 volume percent was added. An increase in RON
and MON was found for all gasoline blends. The gasoline samples having higher RON and MON
were found to have less increase in their octane numbers as compared to gasolines with lower
octane numbers. The sensitivity (RON-MON) was higher for gasoline having higher octane
numbers (Table II) [6].
A-380 is a gasoline produced by Saudi Aramco. The RON of A-380 leadfree gasoline increases
from 83.7 to 85.6 for adding 5 volume percent MTBE and to 95.5 for 30 volume percent MTBE
(Table III). The increase in RON ranges from 1.9 to 11.8 with the addition of MTBE to A-380
gasoline by 5 to 30 volume percent, respectively [3]. In case of A-380 leaded gasoline having lead
(Pb) concentration 0.28 g/liter, only 10 volume percent of MTBE is needed to increase the RON
from 83.7 to 95.5. When 0.4g Pb/liter of gasoline is present, the RON increases to 97.7.
MTBE acts as a high octane blending stock and not as a lead antiknock agent [41]. Up to 15
volume percent of MTBE was added to a base gasoline with RON and MON of 93 and 83,
respectively. The concentration of antiknock compounds (lead alkyls) in gasolines is much lower
than MTBE blends. It has been reported [42] that the average octane number, (RON+MON)/2

also abbreviated as (R+M)/2 increases by 2.3 by the addition of 11 volume percent MTBE to base
gasoline having 90 (R+M)/2. Hence, the blending value, (R+M)/2, of MTBE is 110.9. The
addition of 10 volume percent MTBE into gasoline having RON 98.1 and MON 80.1 increases
both the RON and MON by 23 points [43-45].
It has been observed that the octane number of a 90 RON base fuel can be increased by
using different concentration of MTBE and secondary butyl [12]. The results clearly showed that
the pure MTBE provide more octane to the gasoline as compared to secondary butanol. A chart
has been formulated comparing the incremental gain of average octane number, (R+M)/2, in base
gasoline resulting from the addition of each volume percent oxygenates including MTBE [46].
Based on some of the studies [2,12], 15 percent represented a reasonable concentration of MTBE
in gasoline in terms of octane number increase, change in fuel stoichiometry (air/fuel ratio) and
commercial availability of MTBE.
Fuel sensitivity is defined as the difference between RON and MON. It has been reported
that the fuel sensitivity is a function of MTBE blending octane numbers and it increases with
decrease in the blending octane numbers [27]. This has been shown in Figure 1. The high octane
properties of MTBE are particularly effective in blending with low octane unleaded gasoline
components [32].

Supporting this observation, BOV of MTBE is highest in a low octane

unleaded gasoline. For example, MTBE has a blending octane number of 122 when 15 volume
percent is added to 82 octane unleaded gasoline [32].
The boiling point of MTBE is low. For this reason, MTBE provides much higher front end
octane numbers (FEON) to gasolines. FEON is the octane number of gasoline fraction that boils
below 100 oC. It is reported as RON at 100 C. It becomes important in cold start conditions
when the low boiling parts of gasoline gets a chance to vaporize. When there are no lower boiling
point lead additives to increase FEON, MTBE effectively boost the front end octane. MTBE
gives exceptionally high FEON blending numbers, generally in the range of 135 RON. The FEON

of MTBE is higher than the other gasoline blending components such as butane, reformate,
alkylate and aromatics [34,47]. FEON increases engine efficiency during low speed acceleration
stage.

When MTBE is added to an unleaded gasoline with RON = 88, MON = 81 and RON @ 100
oC = 77 [28,30], its FEON is increased drastically. e.g. when 15 volume percent MTBE is added,
the FEON reaches to 93 while the RON and MON increased to 93 and 86 respectively (Figure 2).
The FEON characterizing the knocking during acceleration shows an unparalleled octane boost.
FEON advantage of MTBE has been reported for a gasoline containing 11 volume percent MTBE
for which the average octane number, (R+M)/2, was increased by 8 [48]. MTBE has a very
favorable effect on FEON as compared to refinery low boiling components at IBP100 oC, which
show considerably lower octane properties. e.g. the gasoline having RON 98.5 has 88.5 FEON as
compared to a gasoline containing 10 vol% MTBE which has similar RON but much higher
FEON (95.5).

The effects of MTBE on the antiknock properties of a large variety of gasolines and gasoline
stocks have been reported. Since the improvement of octane number by an MTBE addition
depends on the composition of the base fuel which contains hundreds of components, accurate
values can only be determined by testing the particular gasoline. For this reason, it is important to
know the hydrocarbon composition of gasoline. That 5, 10 and 20 volume percent MTBE
increase the RON of the premium unleaded gasoline from 91.5 to 92.4, 94.0, and 96.2,
respectively [48]. The front end octane quality improvement has been reported for a typical
premium gasoline with 98/99 RON, 50/55 % distillate at 100 oC containing 0.4g Pb/liter in the
form of tetraethyl lead [6].

MTBE does not decrease the lead susceptibility of the lead alkyl compounds, tetraethyl lead
(TEL), tetramethyl lead (TML) or their blends. MTBE is not affected by the lead level in

gasolines as shown in Figure 3. This study gives information on the production possibility of 93
RON gasoline using base gasolines with given RON, MTBE and lead alkyls. It is possible to
produce unleaded 93 RON gasoline using 88 RON base gasoline and 15 volume percent MTBE.
Leaded 93 RON gasoline can also be produced using 88 RON base gasoline, 10 volume percent
MTBE and 0.1 g Pb/liter as TML. The possibility of blending low leaded or lead-free gasoline of
93 RON using MTBE or lead alkyls can be determined. Since the octane number improving effect
of MTBE concentrated in the low boiling fraction due to its low boiling point, front end octane
improvement of gasolines is increased significantly. The difference between RON and FEON
values drops from 6 to less than 2 when there is 10 volume percent MTBE addition to this
gasoline containing 0.6 g Pb/liter [5].

The TEL response of a typical commercial gasoline containing various amounts of MTBE
has been studied [24]. The RON of a gasoline of RON 92 can be increased to 99 by adding to vol
% MTBE and 0.6 g Pb/liter of gasoline. It has been reported that a reduction in the lead content of
gasoline from 0.6 to 0.15 g/liter will increase the consumption of crude oil in gasoline production
by amounts of 1.73, 2.36, and 4.03 % for gasolines with RON of 94, 96 and 98, respectively [49].
The use of MTBE permits a more effective utilization of petroleum raw material in gasoline
production, thus increasing the gasoline output by 2.6-4% without increasing the volume of crude
oil processed [50]. High aromatic and low olefinic gasolines reduce the blending octane value of
MTBE [9] .
Road Octane Number (RdON) is difficult to obtain, since it is affected by cars and test
conditions. The general equations of RdON and laboratory measured antiknock properties have
been published in the literature [51]. The European Fuel Oxygenates Association (EFOA) carried
out a RdON performance testing of European unleaded gasoline containing MTBE [52].
Oxygenate blends with methanol, cosolvent and MTBE gave superior road octane performance
under accelerating conditions and at low constant speeds compared to reference gasolines. At

high speeds, 3500 to 4500 rpm, RdON advantage of oxygenates diminished giving similar
performance compared to hydrocarbon only gasolines. This shows that MTBE can increase
gasoline FEON by approximately 4 to 7 numbers in contrast to methanol/cosolvents which have a
FEON increase by 3 to 4 numbers.
Vapor Pressure
In addition to the effect of MTBE on gasoline octane numbers, there are other properties
that MTBE influence the performance of gasolines. Most notable are the Reid vapor pressure
(RVP) and distillation temperatures, which are used to control both hot and cold driveability
performance.
Petroleum refiners have been using increased amount of butanes in the United States. Butane
addition increases both the octane number and RVP of the gasoline. Increased use of butane in the
U.S. is the main reason for a 2 to 2.5 psi increase in the RVP over the last decade [4]. The U.S.
Environmental Protection Agency (EPA) is expected to lower gasoline RVP by 2 in order to
reduce the ground level ozone. Table IV is a summary of the blending Reid vapor pressure of
typical gasoline octane components. The blending vapor pressure of MTBE is lower than typical
commercial gasolines [27].
The RVP of MTBE is within the specifications of the gasolines produced by Saudi Aramco
(specification of A-380 gasoline). The RVP of gasoline gradually increases with the addition of
MTBE but remains within acceptable limits (7.119.24) [3]. For example addition of 5 to 30
value percent MTBE increase the RVP from 9.20 to 9.24 as shown in Table V. The direction of
RVP change is either up or down, depending on the original vapor pressure of the base gasoline.
Most authors agree that there is only a small butane loss with MTBE and depending upon the
volatility of the base gasoline, butane may be added to the blend to increase the cost effectiveness
of MTBE [39].

Distillation
MTBE is soluble in any ratio with gasoline and, it boils in the same temperature range like any
other light refinery component. Unlike alcohols, its hydrocarbon compatibility feature does not
permit it to create azeotropic effects on the distillation curve of gasoline. A comparison of
distillation data given in Table VI shows that upon addition of MTBE in gasoline, there is
generally a big decrease in the 50% boiling temperature. Addition of more MTBE produced a
further decrease in the 50% boiling temperature. Ten percent of the distillation temperature of
gasoline is not usually affected by addition of MTBE.
performance is maintained in hot weather.

For this reason, good driveability

The 50 percent temperature of the gasoline is

decreased by addition of MTBE and it usually improve cold engine operation. It has been
reported that addition of MTBE in gasoline has no effect on 10% distillation point, but provide a
decrease of 8, 3 and 30_ C on 50%, 90% and end point (EP) temperature [34,47].

Only butane and MTBE have 50 percent of their temperatures below 93.3 oC but addition of
butane increases the RVP of gasoline. Most of the high octane components produced in a refinery
are usually high boiling point components. Therefore, 50 percent temperature of the gasoline is
more difficult to adjust. ASTM distillation results of the base fuel and the MTBEgasoline blends
(5, 10, 15 and 20) have shown that there is a decrease in percent boiling temperature for all blends
especially a sharp decrease in 50% boiling temperature [3]. This has been shown in Figure 4. The
distillation characteristics of several gasolines and 7 volume percent MTBE-gasoline blends were
determined and the data were presented. Addition of the 7 percent MTBE had rather small effects
on the gasoline distillation temperatures [53].
The ASTM data reported also show that the addition of MTBE changes the distillation
curves of the base gasolines. Indolene is a standard gasoline used in engine testing. The distortion
of these curves caused by MTBE is very small when compared to the

distortion obtained with

alcohol-gasoline mixtures [23]. The effect of adding different amounts of MTBE to a typical

gasoline distillation has been reported [6]. MTBE-gasoline blend curves lie below the gasoline
distillation curve. The greatest distortion in gasoline distillation occurs with methanol and to a
lesser extent, with ethanol. The effect of MTBE is moderately distributed [46]. The effects of 15
percent MTBE on the distillation characteristics of two different gasolines were also studied
recently [54]. The data for the distillation characteristics of gasolines and MTBE blends were
reported in this article.
Stability
The stability of the gasolines can be evaluated by the formation of peroxides during storage.
Long-term oxidation stability tests of three gasolines with 10 percent MTBE blends were carried
out at storage temperatures of up to 43.3 oC [44,45]. Storage at 43.3 oC for a period of six
months can be considered to be equal to approximately two years of storage at ambient
temperature. The gasoline containing MTBE did not produce any peroxides whereas gasoline
alone yielded substantial amount of peroxides. MTBE gasoline blends could be stored for a
minimum of two years under proper antioxidant protection even when prepared with unstable
LCCG gasolines. Oxidation stability of a gasoline with 10 percent MTBE was performed
according to ASTM D-525 test procedure and found no gum formation in excess of 1000 minutes
at 100 C [34].
It has been reported that MTBE is stable during handling and storage, both as a pure
compound and after addition to gasoline [13]. Storage stability was tested after 180 days [6] and
no significant difference of potential gums were found between the base gasoline (98/99 RON, 15
vol% olefins) and base gasoline plus 15 vol% MTBE. Laboratory studies confirmed that peroxides
are not formed with MTBE [2]. Experiments conducted at 60 psig oxygen and 90 oC temperature
showed no titratable peroxide after 15 hours. An extended test performed over a period of two
years indicated no peroxides formation in the MTBE sample exposed to light and air.

Water Tolerance
MTBE gasoline blends show no phase separation in distribution systems in the presence of
water. Solubility of water in MTBE (1.5 wt% water) is very low as compared to alcohols [3]. It
has been indicated that water tolerance is not a problem with MTBE-gasoline blends. Clouding
was observed during the course of preparing MTBE-gasoline blends for testing [23]. However,
clouding was cleared entirely after 24 hours and no other problems such as separation and residue
were observed in the samples. Analysis of a reproduced sample showed that the precipitate was
primarily water and MTBE and the amount was very small.
Water tolerance of gasolines has been studied at 20 volume percent MTBE and 10 volume
percent water. The water was settled in the mixture and there was no haziness. MTBE losses due
to water contact were negligible (200 to 300 ppm in the water). Phase separation in MTBEgasoline blends is not expected to cause problems as in the case of alcohol-gasoline blends [3].
The water solubility of gasolines containing MTBE and secondary butyl alcohol has been studied
[12].

The water solubility of these gasolines is increased considerably with the increase of

secondary butyl alcohol concentration in the blends [12]. There is no hazing problem in a 15
percent MTBE-gasoline blend up to 300 ppm water [35]. Considering the commercial MTBE
containing less than 500 ppm water, a 15 percent MTBE-gasoline blend containing normally 75
ppm water is well below hazing condition. The water holding capacity of MTBE is very high. e.g.
A gasoline containing 15% MTBE was found to have 520 ppm of water compared to 190 ppm
water for a gasoline sample having no MTBE. MTBE-gasoline blends are not as hygroscopic as
alcohol-gasoline blends [66].
IMPORTANCE OF MTBE AND LEAD PHASEDOWN

Regulations regarding reduction in the use of lead in gasolines have had significant impact on
the octane requirements of the gasoline pool. As a result, MTBE received worldwide interest to

supplement refinery-octane quality. The use of MTBE has several advantages. These are high
blending octane number, improvement of engine efficiency low speed acceleration, solubility in
hydrocarbons, No additional precautions in the existing gasoline distribution system, insensitive to
lead level in the gasoline, water tolerance, gasoline like toxicity, no adverse health effects, storage
stability, no unusual problems in driveability, vapor lock tendency, fuel consumption, corrosion and
fuel system material compatibility, reduction of catalytic reforming severity and reduction of
carbon monoxide and hydrocarbon emissions.
Saudi Basic Industries Corporation (SABIC) predicts that demand for MTBE could account
for as much as 10 percent of the gasoline pool by 1995 [55]. Worldwide growth of MTBE
capacity will average more than 20 percent per year during 1989-94 [56,57]. MTBE appears is
one of the most economical ways to add octane while accomplishing environmentally desirable
goals [58].
Industrialized countries regulate the lead content in gasolines. In the United States, the
Environmental Protection Agency (EPA) called for a lead reduction in gasoline beginning from
1973 [7,59,60]. In early March 1985, the EPA ordered the reduction in gasoline lead content to
0.5 g lead/gal by July 1, 1985 and 0.1 g lead/gal by January 1, 1986 [61]. Addition of lead was
regulated by EPA according to the schedule given below:
Step 1. Late 1973, 0.45 g/liter (1.5 g/gal)
Step 2. Mid 1974, introduction of unleaded gasoline
Step 3. July 1, 1985, 0.13 g/liter (0.5 g/gal)
Step 4. January 1, 1986, 0.03 g/liter (0.1 g/gal)
Step 5. January 1, 1988, 0.01 g/liter (0.04 g/gal)
Step 6. After 1990, total elimination of lead in gasolines.
The European Economic Community (EEC) is also phasing out lead. The tendency towards
the reduction of maximum lead content in gasoline is shown in Table VII [6]. EEC requirements

approved in June, 1985 [62,63] are (1). All EEC member states must make unleaded gasoline
available in their territory by October 1989 and (2). All member states are invited to reduce
maximum limit on lead to 0.15 g/liter by October 1989. Western Europe plans to eliminate the use
of lead, but the timing is uncertain. This will probably be completed by the turn of the century
[62]. No leaded gasoline is being used in Japan now [17,64]. Only unleaded 92 RON grade
gasoline is sold in Japan.
The gasoline currently produced in Saudi Arabia is 95 RON. The average lead level in Saudi
gasoline can be reduced from 0.60 to 0.37 g/liter only by operational changes and to 0.25 g/liter
by MTBE blending [7]. Table VIII shows the ability of Saudi refineries to reduce lead content. In
this table, Riyadh and Jeddah refineries are considered to produce regular (83 RON) gasoline in
addition to premium (95 RON) gasoline. Regular grade represents 15 percent of the total gasoline
market.
Table IX shows the lead levels when production of regular grade gasoline is eliminated. The
average lead level, in this case, will increase from 0.37 g/liter to 0.40 g/liter with operational
changes and from 0.25 g/liter to 0.31 g/liter with MTBE blending. The lead phase down schedule
for gasolines in the U.S. is much more advanced than in Western Europe. The reason for this is
the application of catalytic converters in the

U.S. in a short period of time. This movement brought increased demand for unleaded gasoline.
In Western Europe, automobiles with smaller engines can satisfy emission standards without
catalytic converter systems [65].
CONCLUSIONS
The improvement of blending properties by the addition of MTBE depends upon the
composition of the base gasolines which contain hundreds of components in different
concentrations. MTBE blending octane number generally rises with a decrease in the octane

number of base gasoline, a decrease in MTBE concentration of gasoline blends, and an increase in
saturated hydrocarbons of base gasoline. MTBE provides much higher front end octane numbers
(FEON) to gasolines. FEON increases engine efficiency during the low speed acceleration stage.
MTBE does not decrease the lead susceptibility of lead alkyl compounds, tetraethyl lead (TEL),
tetramethyl lead (TML) or their blends.
MTBE has little effect on the distillation and vapor pressure characteristics of gasoline.
There is no evidence of significant azeotrope formation, as is the case when alcohols (methanol or
ethanol) are blended with gasolines. Pure MTBE forms azeotropes with water, but no MTBE
gasoline azeotropes have been reported. MTBEgasoline blends, even in the presence of water,
show no separation problems in the distribution system. Phase separation problems cause
driveability problems in addition to corrosion. MTBE is stable during handling and storage. No
difference in potential gums was found between base gasoline and MTBE blends after an extended
storage.
MTBE appears to be the most economical way to increase octane number while
accomplishing environmentally desirable goals. The average lead content in Saudi Arabian
gasoline is 0.72 g/liter with only premium gasoline production. The United States and Japan
eliminated lead in gasoline after 1990. The EEC is also reducing lead to 0.15 g/liter after 1990
with the exception of Spain, Portugal and Greece where the lead content was reduced to 0.40
g/liter.
Limits on the amount of oxygen allowed in MTBE blends are 2.0 wt% (11 vol% MTBE in
the blends based on 0.737 average specific gravity gasoline) according to the 1981 EPA rule in the
United States and 2.5 wt% (14 vol% MTBE in the blends) according to the EEC directives in
Europe. It is unlikely that more than 3.5 wt% oxygen limit for ethers will be approved, because
nitrogen oxides increase beyond this limit.
ACKNOWLEDGEMENT
The authors wish to acknowledge the support of SABIC and Research Institute of the
King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia for this work under
Project No. 21097.

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Lead phase-out in Western Europe.

Chemical Engineering

FIG. 1. Effect of base fuel sensitivity on the blending octane numbers of MTBE.

FIG. 2. Range of octane number improvement by adding MTBE to an unleaded gasoline.

FIG. 3. Lead susceptibility of MTBE-gasoline blends (production of 93 RON gasoline using

MTBE and TML.

FIG. 4. Effect of MTBE blending on boiling range distribution of gasoline A-380 produced by
Saudi Aramco.

TABLE I
Physical, Chemical and Thermal Properties of MTBE.
Molecular weight
88.15
C/H/O contents, wt%
68.1/13.7/18.2
C/H ratio
5.0
Density, g/cm3
@ 15/4 oC
0.7456
o
@ 20/4 C
0.7404
o
@ 25/4 C
0.7352
@ 30/4 oC
0.7299
Reid vapor pressure, psi
@ 25 oC
4.7
@ 37.8oC
7.8
Boiling point, oC
55.0
Freezing point, oC -108.6
Vapor density, calculated, (air = 1), g/cm3
3.1
Solubility @ 25 oC
MTBE in water, wt%
5.0
Water in MTBE, wt%
1.5
o
Viscosity @ 37.8 C, cSt
0.31
Stoichiometric air/fuel ratio
11.7
Refractive index @ 20 oC
1.3694
Surface tension, din/cm2
19.4
Latent heat of vaporization, Cal/g, @ 25 oC,
81.7
Specific heat, Cal/g. oC, @ 25 oC,
0.51
Lower heating value, Cal/g
8,400
Flammability limits in Air
Lower limit, vol%
1.65
Upper limit, vol%
8.4
Auto ignition temperature, oC
435
o
Flash point, closed cup, C
-25.6
TABLE II
Octane Improvement by the Addition of MTBE to Base Stocks.
Base Gasoline Composition(vol%)
A
B
C

Straight run light gasoline

C5-C6 Isomerate
Reformate, 86/87 RON
Heptanes plus reformate, 94 RON
Reformate, 94/95 RON
Light cat, crack gasoline
Heavy cat, crack gasoline
C3-C4 alkylate
Properties
RVP, psi
Specific gravity @ 15/4 oC
% distilled at 70 oC
% distilled at 100 oC
Olefins, vol%
Aromatics, vol%
Lead content
MTBE Addition(vol%)
Gasoline A
RON
_ RON
MON
_ MON
Sensitivity
Gasoline B
RON
_ RON
MON
_ MON
Sensitivity
Gasoline C
RON
_ RON
MON
_ MON
Sensitivity

0
84.6
79.0

5.6
90.5

83.0
7.5
93.7
84.0

9.7

10

90

50
-50

59.6
22.9
6.1
11.4

5.26
0.751
14
50

40
nil
5
87.0
2.4
80.6
1.6
6.4
92.2
1.7
84.0
1.0
8.2
94.9
1.2
84.6
0.6
10.3

7.96
0.740
36
55

36
nil
10
88.9
4.3
82.4
3.4
6.5
93.7
3.2
85.1
2.1
8.6
96.0
2.3
85.4
1.4
10.6

4.55
0.749
21
53
12
34
nil
15
90.8
6.2
83.8
4.8
7.0
95.2
4.7
86.4
3.4
8.8
97.2
3.5
86.5
2.5
10.7

TABLE III

Base Stock
(Composition
vol%)
Reformate
*P=41.0
N=2.0
A=57.0

MTBE Addition to Reformate and Gasolines.

Base
MTBE
MTBE Blends
Stock
Added
RON
vol%
RON
MON
(R+M)/2
90

5
10
15
20

92.0
93.5
96.0
97.5

87.2
89.5
90.5
91.5

89.6
91.5
93.3
94.5

A-380 Blend
(Unleaded)
P=59.7
N=2.4
A=37.9

83.7

5
10
15
20
30

85.6
88.0
89.6
91.5
95.5

83.1
84.0
84.9
86.1
90.2

84.4
86.0
87.3
88.8
92.9

A-380 Blend
+ 0.15g Pb/liter

87.0

5
10
15

89.5
92.6
95.0

83.5
86.2
89.5

86.5
89.4
92.3

A-380 Blend
+0.28 g Pb/liter

89.5

5
10

91.6
95.5

85.9
89.7

88.8
92.6

A-380 Blend
90.2
5
92.5
+ 0.40 g Pb/liter
10
97.0
* P= Paraffins, N= Naphthenes and A= Aromatics.

87.5
90.5

90.0
93.8

TABLE IV
Vapor pressure of Typical Octane Boosters.
Blending
RVP(psi)
Normal butane
Isopentane
Normal pentane
Commercial gasoline
Base gasoline (No butanes)

60.0
21.0
14.0
11.5
8.5

TABLE V
The RVP of MTBE and MTBE-Gasoline Blends.
MTBE

RVP, psi

8.70

5%
10%
MTBE MTBE

9.20

9.20

Base fuel A-380 +

15 %
20 %
MTBE
MTBE

9.20

9.23

30 %
MTBE

9.24

TABLE VI
Effect of MTBE Addition on ASTM Distillation Curve.
% Evaporated
Base
Base fuel
Base fuel
Fuel
+5% MTBE
+10% MTBE
(C)
(C)
(C)
IBP
29
27
27
10
45
45
44
20
58
58
56
50
108
104
96
70
147
144
147
90
191
189
188
95
206
205
204
EP
218
217
217
TABLE VII

Norway
Denmark

Maximum Lead Content (g/liter) and RON Values in European Countries.

1980
1990
Lead
RON
Lead
RON
Premium
0.40
98
0.15
96
Regular
0.15
90
0.15
91
Premium
0.40
97
0.15
96

Sweden

Regular
Premium

0.40
0.40

91
99

0.15
0.15

91
96

Finland

Medium
Regular
Premium

0.40
0.15
0.70

97
90
98

0.15
0.15

91
96

Netherlands

Regular
Premium

0.45
0.40

91
98

0.15
0.15

91
96

Belgium

Regular
Premium

0.40
0.45

91
98

0.15
0.15

91
96

W. Germany

Regular
Premium

0.45
0.15

90
98

0.15
0.15

91
96

Switzerland

Regular
Premium

0.15
0.40

91
98

0.15
0.15

91
96

Austria

Regular
Premium

0.15
0.40

90
96

0.15
0.15

91
96

UK

Regular
Four stars
Three Stars

0.40
0.45
0.45

86
97
94

0.15
0.15

91
96

France

Two stars
Premium

0.45
0.50

90
97

0.15
0.15

91
96

Italy

Regular
Premium

0.50
0.64

91
98

0.15
0.15

91
96

Spain

Regular
Premium

0.64
0.60

84
96

0.15
0.40

91
96

Portugal

Regular
Premium

0.48
0.64

90
98

0.40
0.40

91
96

Greece

Regular
Premium

0.64
0.50

85
96

0.40
0.40

91
96

Regular

0.50

90

0.40

91

TABLE VIII
Capacities of Saudi Refineries to Reduce Lead Contents with Existing Structure.
Refinery Production
(Barrels/day)
Ras Tanura
Jeddah 13600
Riyadh 43400
Yanbu
Total: 159500

Lead content, g/liter

Lead
Operational
content
changes

64900
0.84
0.30
37600

0.84
0.74
0.10
0.49
0.60

0.60
0.28

0.15
0.37 0.25

With MTBE
Blending
0.42
0.12

TABLE IX
Capacities of Saudi Refineries to Reduce Lead Contents with only Premium Gasoline Production.

Refinery
Ras Tanura
Jeddah
Riyadh
Yanbu
Total:

Lead content, g/liter

Lead
Operational
content
changes
0.84
0.84
0.72
0.49
0.72

0.60
0.35
0.33
0.15
0.40

With MTBE
Blending
0.42
0.15

0.12
0.31