QUALITY SURVEY OF RETAIL AUTOMOTIVE PETROL FUEL ON

ROMANIAN MARKET
Submitted 2 May 2014
Abstract. A petrol fuel quality survey from 48 retail stations belonging to the first top four oil
companies present on Romanian market was performed, being investigated chemical composition
(saturates, aromatics, olefins, alcohols, ethers, oxygen content), density, antiknock resistance,
distillation profile and vapour pressure, and compared with the limits from EU Directives and
Romanian automotive petrol standard. The results were interpreted in terms of conformity with
standards, impact on engine performance and on environment, being also analysed the risk of
contamination. Besides the scientific analysis, the study aims to contribute to a more appropriate
public perception upon petrol quality commercialized in Romania.
Keywords: petrol, physical-chemical properties, quality of fuel, Otto engine,automobile

Introduction
According to predictions,
petroleum based fuels will
be the dominant energy
source for the next decades
in road transportation, 70%
of the car fleet in 2030
being still driven by
internal combustion
engines (World Energy
Booklet 2013). The
environmental concern
imposed a series of very
demanding quality issues
for petrol, difficult to meet
due to variability of crude
oil composition and
production process. The
newcomer countries in
European Union had to
comply more stringent fuel
quality standards than the
national ones before
joining EU (Matijosius and
Sokolovskij 2009),
aligning to two
certification types of
documents which are
product standards and
directives. In the first
category there are included
petrol standards of EU
national laws (SR EN 228)
which are derived from the
most relevant standard for
automotive petrol EN 228
entitled „Automotive fuels-
Unleaded petrol-
Requirements and test
methods”, as well as a
standard for an unitary
procedure for fuel
sampling and testing (SR
EN 14274), ensuring a
statistical confidence of
95% of the test results
towards the fuel quality
commercialized in a grades of petrol both
country. In the second
category there are Fuel
Quality Directives
(Directive 2003/17/EC,
Directive 2009/30/EC)
having less requirements
than national standards, but
imposing for spark engine
fuel a set of parameters
(Table 1), mandatory for all
EU members, focusing on
the control and limitation
of the fuel impact on
people health and
environmental pollution.
Petrol fuel quality in
Romania can be evaluated
in two stages, before and
after joining European
Union in 2007. During pre-
adhesion phase, in 2006
(EU Quality Fuel Report,
2006), there were two
grades of petrol fuel
commercialized on
Romanian market for spark
engines, both unleaded,
having Research Octane
Number (RON) minimum
95, one with sulphur
content lower than 50ppm
(90.1% from production
volume) and the other with
sulphur content lower than
10 ppm (9.9%). In 2006 the
petrol fuel survey on 101
samples showed several
non-conformities such as:
RON mean values were
less than limits, i.e. 93.9
than minimum required 95,
and MON was 84 instead
of minimum required 85,
higher values of aromatics
(39% instead of standard
35%), benzene (1.7%
instead of 1%) and sulphur
content (74 ppm instead of
50 ppm).
After 2007, Romania
revised its fuel quality
systems setting up the Fuel
Quality Monitoring System
(FQMS), meeting the
requirements of EU
Directives. Changes
appeared in petrol quality
being sold in 2011 two
unleaded, with minimum
95 RON, having 5%
biofuel and respectively
with minimum RON 98,
having 5% biofuel. From a
total of 224 petrol samples
only one sample of
unleaded petrol (min. RON
98 and 10 ppm sulphur)
was found as non-
compliant at the parameter
benzene (EU Fuel Quality
Monitoring Summary
2011).The oil companies
active on Romanian market
also introduced internal
standards in surveying fuel
quality in three places: at
the exit of oil refinery, in
fuel deposits and at fuel
stations, in order to avoid
any accidental or illegal
contamination.
In spite of the evident
improvement of petrol
quality in the period 2006-
2011, there are still
complaints of the
customers who believe that
petrol sold in Romania has
a lower quality than that
sold in other EU countries.
Some reasons for lack of
trust could be the older
memories of the drivers on
lower quality of petrol
before joining EU, as well
as several cases of petrol
adulterations presented in
justice (Curierul National,
2003; Bank News, 2007) or
even the placebo effect of
the drivers group opinion.
The objective of the
research work presented in
this paper is to perform a
quality survey of retail
automotive petrol sold on
the Romanian market,
having as main tasks the
investigation of standard
compliance, the analysis of
the non-compliances upon
environment and engine
performance, as well as the
analysis of fuel risk of
contamination.
Table 1. Limits of petrol fuels
in EU Directives
Properties
Research Octane Number,
RON (min.)
Motor Octane Number,
MON (min.)
Vapour Pressure, VP
(kPa, max),summer period
n
admitt
Distillation:
evaporated at 100ºC
46
(%v/v, min.), E100
evaporated at 150ºC
75
(%v/v, min.), E150
Olefins (%v/v, max) 18
Aromatics (%v/v, max) 35
Benzene (%v/v, max) 1.0
Oxygen Content (%m/m, max) 2.7
Methanol, (%v/v, max) 3
Ethanol, (%v/v, max) 5
Iso-Propyl Alcohol (%v/v, max) 10
Tert-Butyl Alcohol (%v/v, max) 7
Iso-Butyl Alcohol (%v/v, max) 10
Ethers containing 5 or more carbon
atoms per molecule 15
(%v/v, max)
Other Oxygenates (%v/v, max) 10
Sulphur Content (mg/kg, max) 10
Lead Content (g/l, max) 0.005
The work is meant to be an
independent study –
performed at [information
deleted to maintain the
integrity of the review
process] – aiming to
contribute to correct public
information on petrol fuel
quality.
1. Experimental
part
1.1. Composition
and fuel test
methodologies
The fuel testing was
accomplished on the
laboratory facilities of
[information deleted to
maintain the integrity of
the review process]. A set
of petrol parameters was
measured using MID-FTIR
spectrometer (IROX 2000,
Gasoline Analyzer from
Grabner Instruments) based
on absorption
measurements, according
to ASTM D 5845, in the
range of 2.7 to 15.4 µm
(Gasoline Analyzer, 2006).
Other properties of petrol
fuel, such as octane
numbers, distillation
properties and vapor
pressure cannot be directly
derived from the IR
spectrum, but can be
predicted with the same
apparatus by using factor
analysis method or multi-
linear regression, based on
the correlation between
absorbencies and
aforementioned properties.
There were investigated 14
relevant parameters
included in EU Directives
and in Romanian standard
(SR EN 228): RON, MON,
VP, distillation profile-in
terms of evaporated
volume at 100ºC (E100)
and evaporated volume at
150ºC (E150), total olefins,
total aromatics, benzene,
oxygen content, methanol,
ethanol, iso-propyl alcohol,
tertiary-butyl alcohol, iso-
butyl alcohol and ethers
with 5 or more carbon
atoms. The accuracies of
the measurements in mass
fractions were 0.5% for
ethers and alcohols, 0.2%
for benzene, 0.1% for
oxygen content, 2% for
aromatics and 1.5% for
olefins. Additionally, there
were measured two
parameters: density and
final boiling point (FBP),
which are relevant in terms
of fuel economy and
engine cleanliness. These
data were compared to
values from product
standards. The accuracy of
distillation temperatures is
0.1ºC, for pressure reading
is 0.1kPa and for density
0.001 g/cm3.
1.2. Survey
methodology
Petrol samples were
collected at filling stations
of four oil companies,
whose brand names were
kept anonymous, as the
study intends to determine
the global petrol quality on
the Romanian market.
The four selected oil
companies, national and
international ones, possess
over 70% from the total
number of filling stations
in Romania, 2236 (Gaz on
Line 2013), and cover
more than 95% from the
customer options (Fuel
Forum 2013). Samples
were taken randomly from
the identified oil
companies, called here A,
B, C and D, starting in May
2011. Each of the four oil
companies (A, B, C, D) has
two types of petrol fuel, a
regular grade having RON
95 (A1, B1, C1, D1) and a
premium grade with RON
higher than 95, marked as
(A2, B2, C2, D2).The total
number of samples was 48,
6 for each type of petrol
fuel. The set of 6 samples
was taken from petrol
stations of A, B, C and D
situated in 6 distinct points
in the central area of
Romania (Braşov, Sibiu
and Făgăraş), the following
results being each a mean
value of the 6 summer period, admitted to
measurements.
2. Results and
discussions
2.1. Investigation of
standard compliance
In the following charts the
dotted lines represent the
limits of petrol fuel
parameters in EU
Directives, according to
Table 1.
Octane numbers
The octane number of the
fuel indicates the antiknock
behaviour of the petrol in
the spark engine. In order
to avoid knock, during all
operation modes of the
engine, the octane number threshold, considering the
of the fuel should be higher measurement accuracy
than octane number (84.5 < 85-0.2).
requirement of the engine.
RON is an antiknock
indicator when the engine
is running at low speeds
and mild loads. The RON
mean values of the 8
grades are presented in
Fig.1. It can be noticed that
the mean value of the
regular grade marked with
index 1 is smaller than the
mean value of premium
grade marked with index 2
(95.25 < 96.85) and the
Fig.2. Mean MON of petrol
overall mean is 96.05, samples
showing a good agreement
with the requirement of the Vapour pressure
petrol standard (95) Vapour pressure is an
marked with dotted line indicator of the petrol
(SR EN 228) . volatility at 37.8ºC,
featuring engine operation
at cold start and warm-up
period. It is constrained
into two limits imposed by
opposite phenomena: a
higher VP provides a rapid
cold start of the engine and
a lower VP prevents the
vapour lock and excessive
evaporative emissions
(MotorGas-Tech-Review
2013). The standard limits
only the maximum value in
Fig.1. Mean RON of petrol
60 kPa and derogated to 70
samples
kPa, but the typical range
MON is an antiknock for automotive petrol is 45-
indicator when the engine 60 (70) kPa. The overall
is running at high speeds, mean value of VP is 60.4
high temperatures and kPa, very close to 60 kPa,
severe loads. The MON the threshold value, as
mean values of the petrol illustrated in Fig.3. No
samples are shown in sample exceeded the
Fig.2. maximum value of 70 kPa.
It can be noticed that the
mean value of standard
grade marked with index 1
is smaller than the mean
value of premium grade
marked with index 2 (85.12
< 85.6) and the overall
mean is 85.36 indicating a
good agreement with the
requirement of the standard
(85), with the exception of
the mean value of samples
C1, which is smaller than
Fig.3. Mean VP of petrol
samples
Distillation profiles
The distillation in standard
is expressed through
minimum imposed values
of evaporated percentage at
100ºC and 150º C, known
also as E100 and E150,
illustrated in Fig.4 and 5.
The minimum percentage
of distilled volume is met,
both for E100 (46%) and
E150 (75%).
Fig.4. Mean E100 of petrol
samples
Fig.5. Mean E150 of petrol
samples
Olefins
For olefin content, no
sample exceeded the
maximum of 18% of the
standard. The total olefins
measured for the samples
are represented in Fig.6,
the overall mean value for
8 types of fuel being
8.16%.
That value confirms the
general tendency of
lowering olefins, thus
limiting olefins in
evaporative emissions and
reducing ozone formation
(MotorGas-Tech-Review,
2013).
Fig.6. Mean olefin content of
petrol samples
Aromatics
There is a tendency to
lower aromatics which will
lead to lower emissions of
carbon monoxide (CO) and
volatile organic compounds
(VOC) in exhaust gas. The
distribution of the mean
aromatic content for the 8
types of petrol can be seen
in Fig. 7, the overall mean
of total aromatics being
33.12%. Only sample A1
has a slight exceeding of
the limit.
Fig.7. Mean aromatic content
of petrol samples
Benzene
One of the aromatic
components, benzene, is
known as the most harmful
compound in petrol due to
its proven carcinogenicity
(InChem 2013) and it has a
distinct limitation in
standard, up to 1%
concentration in volumes.
The limitation of benzene
in petrol will predict lower
benzene in evaporative
emissions and lower VOC
in exhaust gas. The overall
mean of benzene content is
0.77% and its distribution
is presented in Fig.8.
Fig.9. Mean oxygen content of
petrol samples
Ethers
The typical ethers which
can be used in petrol as
substitution components
are MTBE (Methyl Tertiary
Butyl Ether ), ETBE (Ethyl
Tertiary Butyl Ether),
TAME (Tertiary Amyl
Methyl Ether) and DIPE
Fig.8. Mean benzene content (Di-Iso Propyl Ether); by
of petrol samples means of the variation of
ether content, the volatility
Oxygen content and distillation profile of
The newcomer in the petrol the blend can be controlled,
composition is oxygen, ethers being preferred to
introduced by the alcohols. For tested petrol
obligations assumed in EU fuels, the total ether content
to limit the life cycle is revealed in Fig.10.
greenhouse gas emissions The most used ether was
with at least 6 % by the end MTBE which was present
of 2020, mainly by the use in all 8 types of petrol.
of biofuels ( Directive Only two fuels, B1 and C1,
2009/30/EC). have extra ethers in form of
The oxygenated ETBE (B1-6.6%v/v and
compounds could be C1- 4.3%v/v) and TAME
typically alcohols and (B1-1%v/v).The overall
ethers. For the tested fuels mean ether content was
there were found only 10.6%.
ethers and no alcohols. The
oxygen content was
calculated based on the
concentration of the
measured components, as
shown in Fig.9. The
samples did not exceed the
threshold value of 2.7%
and the overall mean of the
8 petrol samples was
1.86%.
Fig.10. Mean ether content of
petrol samples
Density
The typical range of
relative density of petrol
fuels is 0.72 -0.775 which
is included in most of
product standards. As
illustrated in Fig.11, the
measured densities are
within the range and the
overall mean value of
petrol samples (0.743) is
close to the mean value of
the recommended range
(0.747).
Fig.11. Mean relative density
of petrol samples
Considering the engine
performance, the higher the
density of the fuel, the
higher are the mass for the
same volume of fuel and
the heat released during
combustion and the
effective power of the
engine.
Final Boiling Point
FBP is an indicator of the
boiling temperatures of the
heaviest hydrocarbons in
the petrol, being limited to
210 ºC. All the samples
have FBP lower than the
imposed limit and the
overall mean value of FBP
for all tested petrol samples
was 190.4ºC (Fig. 12). The
tendency of lowering FBP
means lower VOC in the
exhaust gas and lower
carbon deposits in the
combustion chamber, but
also less petrol distilled
from one tone of crude oil.
Fig.12. Mean FBP of petrol
samples
2.2. Analysis of the non-
compliances upon
environment and engine
performance
The non-compliances were
detected for octane number,
RON being smaller for test
samples A1, C1, D1 with
(94.9 instead of 95). This is
a minor difference, which
can be accepted if it
considered the accuracy of
the measurement (95±0.2).
For MON, the only non-
compliance is for the petrol
sample C1 (84.5 instead of
85) which must be revised
through a relevant
measurement for knock on
a special purpose engine.
For aromatics, petrol
sample A1 has a higher
content than the limit
(35.5% instead of 35%),
being acceptable, in the
range of the accuracy of
the measurement (35±2%).
Energetically speaking, the
aromatics have a higher
heating value than the other
classes of hydrocarbons,
yielding more useful power
from the spark engine.
Considering octane engine
requirements, the RON and
MON values of several
petrol samples are smaller
than limits, thus meaning contaminated with
that in some operation a heavier
modes it is possible to have hydrocarbon
a very slight knock, which which distills at
should be avoided. From higher
the environmental point of temperatures (for
view a higher aromatic example 2% of
content will produce higher diesel fuel added
VOC in exhaust gas and to petrol rises the
atmosphere. FBP of the blend
with 11ºC);
2.3. Contamination risk - If the distillation
profile does not
Fuel can be altered before respect E100
combustion in spark engine (E100<46%), this
by improper storage, fact can be caused
transport and manipulation by contamination
or accidental or illegal with light
contamination hydrocarbons
(adulteration). The high (hexane) or
level of taxation of auto oxygenates
petrol in Romania (around (alcohols or
50% of its final cost) ethers) in higher
encouraged adulteration by fractions than
means of mixing with other allowed;
refined petrochemicals, - If VP has higher
mainly solvents (heating values than (45-
petrol, kerosene, diesel 70) kPa, it means
fuel, toluene, xylene, that it has
hexane and ethanol),which excessive lighter
may have lower taxes. solvent (such as
The detection of hexane) ; if VP is
contamination is difficult lower than 45, it
as most of the could be caused
hydrocarbons in by contamination
contaminants are also with benzene,
present in the composition white spirit or
of automotive petrol. diesel fuel.
Nevertheless, there are Regarding the tested fuels,
some parameters sensitive taking into account the
to contamination, such as limits of measurement
density, FBP, distillation procedures, the symptoms
profile and VP. of contamination were not
Some non-conformities of identified, so there are no
petrol must be considered clues to indicate any
as symptoms for attempt of adulteration.
adulteration (Takeshita et
al. 2008): Conclusions
- If relative density
is higher than Romanian commitment to
0.79, it may be EU legislation imposed the
suspected meeting of stricter
contamination standards and quality
with an aromatic evaluation procedures. The
product ( benzene, distrust of Romanian
toluene, xylene) or people on current petrol
diesel fuel; quality sold in fuels
- If the FBP is stations is contradicted, in
higher than 210ºC, a greater extent, by the
the petrol could be results of the present
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