FuelVol. 74 No. 12, pp.

1830-1833, 1995
Copyright © 1995 ElsevierScienceLtd
Printed in Great Britain. All rights reserved
0016-2361(95)00158-1 0016-2361/95/$9.50+ 0.00

Antagonism between cloud point and cold

filter plugging point depressants in a diesel
fuel

Jean Marie L~toff~, Pierre Claudy, Despina Vassilakis* and

Bernard Damin*
Laboratoire de Thermochimie Min~rale associ~ au CNRS (URA 116), Institut National des
Sciences Appliqu~es, 69621 Villeurbanne Cedex, France
*Centre de Recherches ELF France de Solaize, BP 22, 69230 St Symphorien d'Ozon, France
(Received 9 September 1994; revised 4 April 1995)

Differential scanning calorimetry (d.s.c.) and thermomicroscopy were used to provide a better
understanding of the antagonistic effect on cold filter plugging point (CFPP) when cloud point depressants
(CPD) and CFPP additives are mixed into a diesel fuel. It is shown that the CFPP achieved by using only
CFPP additive can be attained in the presence of CPD if a small, homogeneous size of crystals of paraffins is
again obtained. Two ways are proposed to obtain this result: modification of the chemical structure of the
CPD, and optimization of the concentration of each component of the blend. In either case a decrease in
efficiency of the CPD is observed, but the antagonism disappears. It is possible to predict the efficiency of
CFPP additives in a diesel fuel containing CPD by evaluation of Tg of the hydrocarbon matrix and
determination of the percentage of light n-alkanes by d.s.c.

(Keywords: diesel fuels; low-temperature properties; additives)

An earlier paper I discussed the interactions between Materials

n-alkanes and two distinct diesel fuel additives: cloud
point depressant (CPD) and cold filter plugging point
(CFPP) depressant. In that paper only the effect of each
additive singly on the cold properties was considered.
Commercial diesel fuels usually contain a CFPP
depressant which modifies the crystal growth of the
n-alkanes that precipitate on progressive cooling,
thereby lowering the temperature at which the fuel
filter in a diesel engine becomes blocked by the continued
growth of the crystals.
Experiments have shown that although effective in
lowering the cloud point, CPDs can seriously impair the
performance of CFPP additives in some diesel fuels. This
antagonism appears to depend on several factors, which
include the chemical structure of the CPD, the type of
diesel fuel and the relative concentrations of CPD and
CFPP additive present.
In this work, differential scanning calorimetry (d.s.c.)
and thermomicroscopy were performed to provide better
understanding of the antagonism with respect to cold
filter plugging point when CPD and CFPP additive are
mixed into a diesel fuel.
EXPERIMENTAL
Methods
The apparatus and experimental procedure for d.s.c.
and thermomicroscopy have been previously described 1'2.
Dieselfuels. Sixteen European diesel fuels were used.
They were characterized by distillation analysis accord-
ing to method ASTM D2887 and by density at 15°C
(Table 1).
CP depressants. Additives were prepared by the
polymerization of linear ~-olefins with acrylic, vinyl
and maleic unsaturated compounds at atmospheric
pressure. They lower the cloud point by specific associa-
tion with the heavy n-alkanes which precipitate at the
cloud point, forming soluble complexes.
In this study, eight additives were used, with different
chain lengths (Cl8 to C24) and different molar ratios.
Their molecular weights were determined by g.p.c, using
polystyrene as a reference; they varied from 2250 (CPD
1) to 11 000 (CPD 8).
CFPP depressant. Ethylene-vinyl acetate copolymer
(MW = 10000) was used. This additive develops weak
interactions and cannot strongly modify the solubility
of n-alkanes. Its mode of action is to reduce the size of
the n-alkanes crystals by increasing the number of nuclei
in the fuel.
RESULTS A N D DISCUSSION
Thermal characterization of diesel fuels
By means of d.s.c, on heating and cooling, several

1830 Fuel 1995 Volume 74 Number 12

 Point depressants in diesel fuel: J. M. L~toff6 et al.

Table 1 Distillation analysis (ASTM D 2887) and density of diesel

fuels ACFPP

Temperature (°C) at distillate yield (%) of Density 15

Fuel at 15°C
no. I.b.p. 10 20 50 90 95 F.b.p. (gcm -3)

1 179 219 239 280 337 359 373 0.845 10

2 166 199 214 257 336 359 373 0.843
3 189 225 239 277 339 355 373 0.844
4 206 235 259 290 344 357 370 0.840 5
5 177 196 206 259 344 363 373 0.836
6 191 241 255 286 338 352 373 -
7 218 252 262 285 344 357 369 0.858
8 179 234 255 290 345 358 367 0.872 0
9 203 235 247 281 353 371 386 0.843
10 188 234 254 287 345 359 372 0.841 0%C13
11 166 195 219 287 354 368 373 0.844 ! I I I ~ '~
12 172 205 217 267 346 365 383 0.5 1.0 1.5 2.0 2.5
13 169 215 235 281 336 352 366
14 162 200 221 277 338 352 369 0.838 Figure 1 Change in CFPP versus content of light alkanes (wt% C<I3)
15 192 227 240 276 337 351 370 0.840 in different diesel fuels blended with 250mgkg -I of CFPP additive
16 182 214 226 266 337 354 365 0.843 and 500 mg kg ~ of CP depressant

cFPp . 1 .. /
Table 2 Thermal properties for diesel fuels with very antagonistic
behaviour

Total Change 15
Fuel Tg C<l 3 n-alkanes Tc in CFPP
no. (°C) (wt%) (wt%) (°C) (°C)

3 - 117.2 0.53 12.3 -4.3 +10 10

4 -115.9 0.10 12.2 -3.4 +10
6 -115.8 0.05 12.3 -4.1 +10
9 -117.7 0.55 14.8 -3.7 +8 5
10 -115.5 0.40 14.0 -2.4 +10
7 -110.4 0 11.8 -2.7 +17
8 -113.9 0 11.5 -2.8 +12
0

J •• Tg(ocI
! I I
Table 3 Thermal properties for diesel fuels with neutral orsynergistic -125 -120 -115
behaviour

Total Change Figure 2 Change in CFPP versus glass transition temperature Tg of

Fuel Tg C<j 3 n-alkanes Tc in CFPP different diesel fuels containing 250mgkg ~ of CFPP additive and
no. (°C) (wt%) (wt%) (°C) (°C) 500 mg kg 1 of CP depressant

ll -125.6 1.20 15.1 +l.1 -2

5 -126.4 2.25 13.7 -2.3 -2
2 -125.3 1.70 11.9 -7.3 +2
• temperature of onset of crystallization, Tc, and
12 -125.0 2.10 17.1 -1.6 0 amount of precipitated n-alkanes versus temperature.
13 -121.5 1.40 16.2 -5.8 +2
Tables 2-4 report the values of most of the above
properties and the increase in CFPP corresponding to a
blend of 250mgkg-J of CFPP depressant with
Table 4 Thermal properties for diesel fuels with slightly antagonistic 500mgkg -1 of a conventional CPD (CPD 4). No
behaviour correlation was found between the increase in CFPP
and Tc or total percentage of n-alkanes. However,
Total Change
Fuel Tg C<~3 n-alkanes T¢ in CFPP
correlations were observed between the increase in
no. (°C) (wt%) (wt%) (°C) (°C) CFPP and the percentage of light n-alkanes (C<13),
Figure 1, and Tg, Figure 2; the correlation coefficients
1 -119.7 0.85 13.5 -5.1 +7 were 0.89 and 0.86 respectively.
15 -121.5 0.80 13.9 -7.5 +8
14 -124.9 1.15 14.9 -4.9 +5 These results show that it is possible to predict the
16 -124.6 0.63 11.4 -6.0 +5 efficiency of CFPP additives in diesel fuels containing a
CPD:
• if Tg is below - 125°C and C<I 3 is > 1 wt%, a neutral or
properties can be easily obtained with good synergistic effect is obtained;
reproducibility 2'3 such as: • if Tg is above -120°C and C<13 is <0.6wt%, a very
antagonistic behaviour occurs.
• transition glass temperature, Tg, which characterizes
the hydrocarbon matrix The diesel fuels that do not fall into either of these two
• total percentage of n-alkanes in the fuels classes show slightly antagonistic behaviour.
• percentage of light alkanes (C<13) However, it is not easy to explain these observations. It

Fuel 1995 Volume 74 Number 12 1831

Point depressants in diesel fueL J. M. L#toff# et al.

CFPP(*CI FUEL 3

I!/~ ~ CFPP add + CPD1 -1 T = -8°C

250 p.W
/ I \\ - - - - CFPP add + CPD2 -3 CFPP = 0°C
q\\
!\-
!
FUEL 3 + CFPPadd + CPD1

T = -11 °C

CFPP = -1 °C
I~ - - - - CFPP add + CPD4 -5
f~t,i ~` ~ , ' N ~ CFPP add + CPD5 -6
I ~l t.I m'~ ,..~

FUEL 3 + CFPPadd + CPD5

T = -11 °C

t~ /~ CFPP add -15 CFPP = -6°C

- - - - C F P P add + CPD8 -23

I FUEL 3 4- CFPPadd + CPD7

I
I
T = -11 ~O

CFPP = -14°C
T(°C)
I I I m
-5 -10 -15

Figure 3 D.s.c. curves on cooling of an 'antagonistic' fuel blended FUEL 3 + CFPPadd

with 250mgkg -l of CFPP additive and 500mgkg -J of different CP
depressants T = -1&C

CFPP = -15°C

Table 5 Results for fuel 3 blended with CFPP additive (250 mg kg I) 100 ~tm
and different CPDs (500mgkg -I)

CPD Number of Lowering of Figure 4 Photomicrographs of an 'antagonistic' fuel blended with

no. CFPP (°C) peaks cloud point (°C) 250mgkg -z of CFPP additive and 500mgkg J of different CP
depressants
None -15 1 -0.35
1 -1 1 1.95
2 -3 1 2.25
3 -5 3 2.45 study, eight CPD were used, at the same concentration
4 -5 3 2.95 of 500mgkg -z in the antagonistic diesel fuel 3. The
5 -6 3 2.25
6 -7 3 2.40
concentration of CFPP additive was also constant at
7 -14 1 1.75 250 mg kg -1 .
8 -23 1 1.40 The d.s.c, curves on cooling are shown in Figure 3.
Three kinds of thermal behaviour were obtained:
(1) one wide precipitation peak with a large slope with
is well known that a low value of Tg and a major CPD1 and CPD2, corresponding to rapid precipita-
percentage of light n-alkanes increase the solubility of tion and simultaneously a marked change (12-14 °C)
the hydrocarbon matrix and simultaneously modify the in CFPP;
viscosity of diesel fuel. Viscosity experiments are there- (2) three precipitation peaks with CPD4 and CPD5, as
fore in progress. also with CPD3 and CPD6, corresponding to an
change of 8-10 °C in the CFPP;
Masking of antagonism in diesel fuels (3) only one slight precipitation peak with CPD8, as
To solve the problem of antagonism without altering with CPD7, without any antagonistic effect, even a
too much the effect of CPD on cloud point, two methods synergistic action being obtained with CPD8.
can be considered:
The results of the d.s.c, determinations are given in Table
• modification of the chemical structure of the CPD; 5.
• optimization of the quantity and ratio of CFPP Photomicrographs obtained by thermomicroscopy at
additive and CPD in the formulation. temperatures close to the CFPP are shown in Figure 4.
Depending on the chemical structure of the CPD, it is
Modification of CPD chemical structure. In this possible to observe:

1832 Fuel 1995 Volume 74 Number 12

 Point depressants in diesel fuek J. M. L6toff~ et al.

Nevertheless, the cloud point can be lowered by 1.7°C, as

Lowering of cloud point (*C)
shown in Table 5.
1 peak 3 peaks 1 peak
Optimization of formulation. A total concentration
of 750mgkg I for the CFPP additive and CPD4 was
used, in the same antagonistic diesel fuel 3. The results
are given in Table 6. An optimal formulation was found:
3.0 Is)
450mgkg -1 of CFPP plus 300mgkg -1 of CPD4. One
peak of precipitation and a lowering (~2°C) of the cloud
point were obtained. Simultaneously a CFPP of - 2 1 ° C
was achieved and homogeneous precipitation of small
1.5 crystals was observed.

CFPP(°C) CONCLUSIONS
I I I I
0 -5 -10 -15 -20 The results reported provide a basis for an explanation
of the antagonism in some diesel fuels. As previously
Figure 5 Correlation between the lowering of CP, CFPP and d.s.c.
curves and thermomicroscopy observations
described 1, the size and shape of n-alkane crystals are
different when CPD and CFPP additives are added to the
fuel:
• CPD develops well-separated crystals, but they are
Table 6 Results for fuel 3 blended with CFPP additive and CPD4 in larger than in the undoped diesel fuel;
different amounts
• CFPP additive always produces the same behaviour:
CFPP CPD4 CFPP Number of Lowering of very small crystals (1-3 #m) are observed.
(mgkg I) (mgkg 1) (°C) peaks cloud point (°C)
Using blends of CFPP additive and CPD, an inter-
250 nil -15 1 -0.40 mediate size is obtained and therefore the CFPP
250 500 -5 3 2.60
300 450 -5 3 2.40
increases.
350 400 -7 3 2.25 The CFPP level achieved by using only CFPP additive
400 350 -7 3 2.10 can be attained in the presence o f a CPD ifa small crystal
450 300 -21 1 1.95 size is again obtained. Two methods can be used:
500 250 -20 1 1.80 modification of the chemical structure of the CPD or
600 150 -22 1 1.40
700 50 -24 1 0.80 optimization of the concentration of each component of
the blend. In either case, a decrease in efficiency of the
CPD is observed but the antagonism disappears.
The efficiency of CFPP additives in a diesel fuel can be
• large crystals (20-30 #m), correlated of course with an
predicted by considering the thermal parameter Tg and
increase in CFPP;
the percentage of light n-alkanes determined by d.s.c.:
• a mixture of large and small crystals ( 2 - 5 # m ) ,
corresponding to an increase of 8-10°C in CFPP; • if Tg is below -125°C and C<13 is >1 wt%, a neutral or
• small crystals (2 5#m) with a homogeneous size synergistic effect is observed;
distribution, corresponding to the absence of any • if Tg is above -120°C and C<13 is <0.6wt%, a very
antagonistic effect. antagonistic behaviour occurs.
The d.s.c, results and the microscopic observations are
plotted versus the corresponding values of CFPP in
Figure 5. It is obvious that the disappearance of the REFERENCES
antagonistic effect corresponds to:
1 Claudy, P., L6toff6, J. M., Bonardi, B. and Vassilakis, D. Fuel
• a weak slope of precipitation, i.e. a slow rate of 1993, 72, 821
2 Claudy, P., L6toff+, J. M., Neff, B. and Damin, B. Fuel 1986, 65,
crystallization into the fuel; 861
• only one peak during precipitation, corresponding to a 3 Claudy, P., Bosselet, F., L&off& J. M. and Valentin, P. Thermo-
homogeneous distribution of small crystals. chim. Acta 1983, 70, 19

Fuel 1995 Volume 74 Number 12 1833