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Fuel
journal homepage: www.elsevier.com/locate/fuel
h i g h l i g h t s
g r a p h i c a l a b s t r a c t
Finished gasoline, total aromatics, oxygen, rapid refracto-densimetric test method, unbalanced gasoline,
adulteration.
0,351
0,349
Normal-80
0,347
0,345
sRLL
Regular-92
0,343
RI=1,0545
0,341
Premium-95
0,339
0,337
RI=1,0522
sR LL =0,3373
0,335
1,04 1,042 1,044 1,046 1,048 1,05 1,052 1,054 1,056 1,058 1,06
RI
a r t i c l e
i n f o
Article history:
Received 1 March 2014
Received in revised form 26 September
2014
Accepted 15 October 2014
Available online 6 November 2014
Keywords:
Index of refraction
Density
Oxygenate
CottonMouton effect
Adulteration
a b s t r a c t
This paper presents routine refracto-densimetric indicators which may be used to identify unbalanced
automobile gasoline and falsications (surrogates). These criteria are supposed to reduce considerably
the amount of testing via standard chromatographic and spectroscopic methods. Refracto-densimetric
method for controlling the limiting weight content of oxygen is based on substantial difference between
specic refractions of oxygenates and hydrocarbon gasoline components. Application of the refractive
intercept which is additive in the volume fractions of components and constant for different homologous
series of hydrocarbons allowed to establish its maximum value, the excess of which identies a gasoline
with a high content of aromatic hydrocarbons. In addition, the excess of refractive intercept of certain
limit value can also indicate the possible presence of conjugated diolens in gasoline and bicyclic arenes.
2014 Elsevier Ltd. All rights reserved.
Corresponding author at: Laboratory of Chemistry and Petroleum Geochemistry, A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientic Center of the
Russian Academy of Sciences, 420088, Arbuzov St., 8, Kazan, Russia.
http://dx.doi.org/10.1016/j.fuel.2014.10.042
0016-2361/ 2014 Elsevier Ltd. All rights reserved.
1. Introduction
The focus of monitoring light petroleum products, in particular
the motor gasolines, is in the quantitative determination of various
groups of hydrocarbons. In motor gasolines, besides the products
of direct distillation of crude oil and products of secondary processes of its processing (catalytic cracking, reforming process,
etc.), there are oxygenates added during the compounding of commercial gasoline in order to increase the octane number and the
complete combustion.
The arsenal of modern methods for determining the composition of petroleum products is very wide [16]. Since petroleum
products are multicomponent mixtures, many physical methods
in the study of such mixtures require special approaches, both in
staging the experiment, and in its subsequent interpretation. In
some cases, when assessing the quality of petroleum products, it
is convenient to use the integral (i.e. non-spectroscopic and nonchromatographic) physical methods, in which a particular property
of a substance or mixture is represented as a numerical (integral)
value. These methods can be referred to, in particular, as magnetic
birefringence (CottonMouton effect) [79], refractometry [10],
tensiometry, viscosimetry, densimetry [11] and dielectrometry
[12]. The sensitivity of each method to a particular group of compounds (hydrocarbons) allows on combining them (using together)
to determine the content of mixtures, to evaluate their performance properties and their identication. The need to develop
the methods of rapid identication of petroleum products is dictated by the fact that the volume of counterfeit products, especially
in the motor fuels market, remains signicant [1316]. It is generally known that one way of falsication of motor fuels is replacement of components to cheaper and environmentally hazardous
ones, which leads to signicant deterioration in performance properties of fuels, and to increased carbonization, thereby to resource
reduction of the engine.
The problem of improving the quality of motor fuel is of particular importance also due to the fact that the constantly increasing
requirements of international standards for environmental
properties of fuels [17], which makes the development of methods
for rapid identication of petroleum products an extremely urgent
task. Implementation of such control methods is of extreme interest both for fuel inspection, customs and immediate consumers,
because these methods allow to detect counterfeits and doubtful
quality gasolines subjected to subsequent verication by the standard methods recommended by fuel standards Euro-4 and Euro-5.
Important quality parameters of conventional gasolines are the
total content of aromatic hydrocarbons limited by fuel standards
Euro-4 and Euro-5 with the value not greater than 35 vol%, and
the total oxygen content not more than 2.7 wt%. In order to make
these parameters standards a series of spectroscopic and chromatographic ASTM-methods were recommended. Increased content of aromatic hydrocarbons results in incomplete combustion
of the fuel, to the growth of soot formation and as a consequence,
to increased toxicity of emissions into atmosphere. In turn, the
increased oxygen content (more than 2.7 wt%), due to the presence
of oxygenates (dialkyl ethers and lower aliphatic alcohols) in gasolines, leads to the increase of toxic aldehydes and ketones content
in combustion products, to the reduction of the heat of fuel
combustion, to increased fuel consumption, to delamination of
gasoline in contacting with moisture, to swelling of non-metallic
parts of fuel supply pipe. Possibility of the routine assessment of
the quality of gasoline on the total content of aromatic hydrocarbons will also allow to identify gasoline with a high content of conjugated diolens and with unacceptable in gasoline bicyclic arenes
(e.g. naphthalene and its derivatives), added to surrogate fuels to
increase the octane number. The presence of the latter in gasoline
95
RI n d=2;
sRLL n2 1=n2 2 d
sRGD n 1=d:
RImix
k
X
RIi v i RI1 v 1 RI2 v 2 . . . RIk v k
i1
nmix
k
X
ni v i n1 v 1 n2 v 2 . . . nk v k
i1
dmix
k
X
di v i d1 v 1 d2 v 2 . . . dk v k ;
i1
sRmix
k
X
sRi wi sR1 w1 sR2 w2 . . . sRk wk :
i1
1=dmix
k
X
wi =di w1 =d1 w2 =d2 . . . wk =dk :
i1
The given dependences Eqs. (5), (6) and (8) are derived from
supposition that the mixture volume equal to the sum of volumes
of the starting components, which is performed for hydrocarbon
mixtures with a sufciently high accuracy. In case of deviations
of dependencies Eqs. (5)(8) from linearity in terms of volume or
weight fractions of the components of the binary (or pseudobinary)
mixture using these equations in software refracto-densimetric
analyzers, there can be used different approximating equations
that best describe the properties of mixtures in a wide range of
compositions. Among these dependencies:
Hyperbolic equation (Eq. (9)) [10]:
96
where qi, qmix physico-chemical properties of the starting individual components and the mixture, for example, index of
refraction n, density d or its inverse value 1/d, specic refraction
sR or refractive intercept RI, c1 and c2 volume v1, v2, weight w1,
w2 or the molar x1, x2 fractions of components, respectively
(c1 = 1 c2), K parameter obtained by statistical processing
of data array ciqi;
Korzheniovsky equation (Eq. (10)) (cited by [10])
10
qmix q1 c1 q2 c2 c1 c2
m
X
Ai c1 c2 i ;
11
i0
12
14
where K1, K2, l, p, r, s adjustable parameters. First approximations for the coefcients K1 and K2 during iterations are chosen
equal in absolute value but opposite in sign, and for the exponents l, p, r, s the rst approximation is taken to be equal 1. These
expressions can be used in solving problems related to the definition of the binary (pseudobinary) mixture on any of physico-chemical properties qmix and properties of the initial
components q1 and q2.
15
5b;
15
16
wmax 0:027=wO=oxygenate
2. Experimental procedure
Heptanetolueneisobutyl alcohol mixtures, modeling gasolines, were prepared from reagents qualied as pure according
to the Russian standards TU 2631-023-44493179-98, TU 2631007-44493179, and GOST 6016-77, respectively.
Index of refraction nD20 measurements of ternary mixtures were
performed on IRF-23 refractometer, densities d20 were determined
pycnometrically at 20 C. For additional control of gasoline to the
total content of aromatic hydrocarbons by the method of magnetic
birefringence (CottonMouton effect) on the installation MOBIN
(IPL-456) described in [7,8,11], magneto-optical benzene index
(BIN) representing the ratio of the gasoline magnetic birefringence
(CottonMouton constant) to the magnetic birefringence of benzene determined under the same conditions (t = 20 C, HeNe laser
k = 632.8 nm) was measured. Magneto-optical benzene index BIN
is associated with the volume fraction of aromatic hydrocarbons
varomatics in gasolines by Eq. (16)
17
18
97
nD20
d20
Moxygenate
wO/oxygenate
wmax
sRLL
sRGD
RI
MeOH
EtOH
i-PrOH
tert-BuOH
i-BuOH
MTBE
ETBE
MTAE
DIPE
Dibutyl ether
Dipentyl ether
Diisopentyl ether
Dihexyl ether
Diheptyl ether
Dioctyl ether
1.3288
1.3611
1.3776
1.3878
1.3970
1.3690
1.3794
1.3891
1.3679
1.3992
1.4119
1.4085
1.4204
1.4275
1.4327
0.7914
0.7893
0.7855
0.7887
0.8021
0.7405
0.7465
0.7672
0.7241
0.7689
0.7833
0.7770
0.7936
0.8008
0.8063
32.0
46.1
60.1
74.1
74.1
88.1
102.2
102.2
102.2
130.2
158.3
158.3
186.3
214.4
242.4
0.500
0.347
0.266
0.216
0.216
0.182
0.157
0.157
0.157
0.123
0.101
0.101
0.086
0.075
0.066
0.0540
0.0778
0.1014
0.1250
0.1250
0.1487
0.1725
0.1725
0.1725
0.2197
0.2671
0.2671
0.3144
0.3618
0.4091
0.2569
0.2804
0.2932
0.2991
0.3002
0.3047
0.3099
0.3083
0.3108
0.3147
0.3176
0.3178
0.3191
0.3209
0.3221
0.4155
0.4575
0.4807
0.4917
0.4950
0.4983
0.5083
0.5071
0.5081
0.5192
0.5259
0.5257
0.5297
0.5338
0.5366
0.9331
0.9665
0.9849
0.9935
0.9960
0.9988
1.0062
1.0055
1.0059
1.0148
1.0203
1.0200
1.0236
1.0271
1.0296
0.35
y = -0,151x + 0,3327
0.33
sRLL
0.31
0.29
0.27
0.25
0
0.1
0.2
0.3
0.4
0.5
0.6
wO/oxygenate
Fig. 1. Dependence of specic LorentzLorenz refraction sRLL(oxygenate) of dialkyl
ethers and lower aliphatic alcohols versus weight fraction of oxygen wO/oxygenate
(data from methanol CH4O to dioctyl ether C16H34O).
19
20
23
22
0:999; s0:00077
0.33
21
sRoxygenate
0.31
The above correlations indicate that these refractometric characteristics are quite sensitive to the oxygen content in the oxygenate and can be used in the development of refracto-densimetric
rapid method to control the oxygen content in gasolines. Free
terms of Eqs. (19)(21) represent the average specic refractions
sRLL(alkyl), sRGD(alkyl) and the average refractive intercept RI(alkyl)
hydrocarbon fraction of oxygenate. Moreover, the specic Lorentz
Lorenz refraction sRLL(alkyl) of the hydrocarbon fraction in (19)
turns out to be equal 0.3327 that is within the range of specic
refractions naphthene hydrocarbons sRLL(cyclohexane) = 0.3295,
0.29
0.27
0.25
0
50
100
150
200
250
Moxygenate
Fig. 2. Dependence of specic LorentzLorenz refraction sRLL(oxygenate) versus the
molecular weight of oxygenate.
98
Table 2
Calculated specic LorentzLorenz refractions sRLL of hydrocarbonoxygenate mixtures with the content of the latter in the mixture in the amount wmax, providing 2.7 wt% of
oxygen.
Hydrocarbon component
sRhydrocarb
Hexane
Heptane
Hexene-1/heptane (18/82)
i-Octane
Cyclohexane/heptane (1/4)
Toluene/heptane (35/65)
Catalytic (ally cracked) gasoline
sRAVR =
0.3467
0.3449
0.3453
0.3438
0.3416
0.3426
0.3388
0.3434
EtOH
i-PrOH
t-BuOH
i-BuOH
MTBE
ETBE
MTAE
DIPE
0.3419
0.3402
0.3405
0.3391
0.3370
0.3380
0.3344
0.3387
0.3416
0.3399
0.3403
0.3388
0.3368
0.3377
0.3343
0.3385
0.3413
0.3397
0.3400
0.3386
0.3367
0.3376
0.3342
0.3383
0.3408
0.3392
0.3395
0.3382
0.3363
0.3371
0.3338
0.3378
0.3409
0.3393
0.3397
0.3383
0.3364
0.3373
0.3340
0.3380
0.3405
0.3389
0.3393
0.3380
0.3361
0.3370
0.3337
0.3376
0.3404
0.3389
0.3392
0.3379
0.3361
0.3370
0.3338
0.3376
0.3401
0.3386
0.3389
0.3377
0.3358
0.3367
0.3336
0.3373
0.3405
0.3390
0.3394
0.3381
0.3363
0.3371
0.3340
0.3378
Table 3
Refractive intercepts of different homologous series of hydrocarbons [18].
Hydrocarbons
Refractive intercept RI
Parafnic
Saturated monocyclic (naphthenes)
Monoolens
Diolens
Conjugated diolens
Aromatic monocyclic
Naphthalenes
1.0458
1.0395
1.0521
1.0613
1.0809
1.0626
1.1082
24
Table 4
Limiting values of refractive intercepts RI of gasolines containing 35 vol% of aromatic hydrocarbons depending on the composition of parafnnaphthenic and olen parts and on
the presence of oxygenate.
Characteristics of non-aromatic gasoline components
Without olens
Monoolens (18 vol%)
Or diolens (18 vol%)
Or conjugated diolens (18 vol%)
Without oxygenate
Composition of parafnnaphthenic fraction of
gasolines
Parafns/naphthenes 4/1
Parafns
Parafns/naphthenes 4/1
Parafns
1.0451
1.0465
1.0481
1.0517
1.0457
1.0469
1.0485
1.0521
1.0509
1.0522
1.0539
1.0565
1.0517
1.0528
1.0545
1.0580
99
0.3500
1,06
1,055
5
1,05
RI
4
3
1,045
EURO- 4, 5
Conditioned mixtures
0.3400
increased
carbonization,
incomplete
combustion,
unbalanced
gasoline
0.3300
sRLL
0.3200
sRLL=0,3376
High oxygen
wO/mixture>0,027
High both
parameters
0.3100
2
RI=1,0517
0.3000
1,04
0.2900
0.990
0,1
0,2
0,3
0,4
0,5
Line 3
Line 4
Line 5
1.020
1.030
1.040
1.050
1.060
1.070
0,6
Line 2
1.010
RI
0,351
0,349
Normal-80
0,347
0,345
sRLL
Line 1
1.000
var
1,035
Regular-92
0,343
RI=1,0545
0,341
0,339
Premium-95
0,337
0,335
RI=1,0522
sR LL =0,3373
1,04 1,042 1,044 1,046 1,048 1,05 1,052 1,054 1,056 1,058 1,06
RI
Fig. 5. Refracto-densimetric identication card of motor gasoline in the coordinates
RIsRLL with the boundaries of gasoline, conditional on the total content of
aromatics and total oxygen content.
100
Acknowledgements
The authors are grateful to the Russian Foundation for Fundamental Research (RFFR) for nancing the manufacture of a prototype of magneto-optical analyzer of hydrocarbon fuels MOBIN,
which was used in this work, to executive management of the
Republican Inspection on fuel quality control of the Republic Tatarstan (Russia), providing the opportunity for validation of the new
refracto-densimetric method for assessing the quality of motor
gasoline by the total content of aromatic hydrocarbons and the
total content of oxygen in a representative set of samples.
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