Chemical stability of diesel fuels and sediment formation therein

1. Evaluation

following

of the chemical stability of diesel fuels by the kinetics of sediment formation

M. I. Boneva,

Zh. D. Kalitchin, SI. K. lvanov, S. K. Tanielyan, P. T. Georgiev, A. Ivanov* and K. Kanariev*

Institute of Organic Chemistry, Bulgarian Academy of Sciences, Sofia 17 13, Bulgaria *Institute of Petrorefining and Petrochemistry, SF Neftochim, Bout-gas 8000, Bulgaria (Received 73 May 1991; revised 20 September 1997)

The chemical stability and the kinetics of formation of insolubles in model diesel fuels and of the different components used in their formulation are studied at elevated temperatures. The parameters which change during the accelerated ageing are studied. A new method is developed to follow the kinetics of formation

of total insolubles in diesel fuels using light scattering on the basis of nephelometry. Comparing the experimental data and values of the initiation rate constant for total insolubles formation calculated by the kinetic approach showed that the process is not just a polymerization reaction. Sulphur content has a significant influence on the formation of total insolubles and should be considered in the formulation of diesel fuels.
(Keywords: diesel; kinetics; sediment formation)

The possibility of long term storage of diesel fuels is determined by their physical and chemical stability. To evaluate chemical stability the following are studied : acid number, oxygen absorption, optical density, amount of insoluble gum, amount of total insolubles, etc. The last two parameters are considered the most important factors in the stability of diesel fuels. It has been shown by several authors that the auto-oxidation of hydrocarbons to hydroperoxides is the main reaction leading to the formation of soluble and insoluble gums 2- l3 . The decrease in chemical stability of fuels is connected to the presence of mono- and di-olefins and alkyl aromatic hydrocarbons with short side chains7v8. A synergistic action has been found to occur between mono- and di-olefinsO. The influence of sulphur content on the stability of diesel fuels is studied in Ref. 14. Our data show that there are two basic processes leading to the formation of total insolubles in diesel fuels 5 : formation of gum as a result of thermal and chemical processes in the absence of atmospheric oxygen ; and oxidation of hydrocarbons by atmospheric oxygen with the formation of gum and total insolubles. We consider that the basic shortcoming for methods described in the literature for studying the chemical stability of diesel fuels is the fact that the experiments are not carried out in the kinetic region. We were unable to find any data in the literature concerning the determination of the kinetics of formation of total insolubles in diesel fuels at elevated temperatures. Such studies have been published recently for jet fuels16. Ritchie concluded that standard methods are not useful for predicting the storage stability of diesel fuels.
00162361/92/04043746 !C> 1992 Butterworth-Heinemann

Our studies18 show that the logarithm of the rate of formation of total insolubles shows a linear dependence with the inverse of temperature (Arrhenius dependence) over a wide temperature range (393-433 K) 5,18. Therefore, the processes in our method for studying the rate of total insolubles formation proceed in the kinetic region (with no significant diffusion or other factors involved). The measured activation energies of two samples (2 and 8) are of the order of 70 kJ mol- which proves that chemical processes but no diffusion occur18. The purpose of this paper is to study the chemical stability and the kinetics of formation of total insolubles both in model diesel fuels and of the different components used for their formulation, at elevated temperatures. The parameters which change during the accelerated ageing are studied in order to obtain a suitable parameter to evaluate and predict chemical stability. EXPERIMENTAL The basic physico-chemical characteristics of the components used in the production of diesel fuels are given in Table I. They include the following fractions obtained by the atmospheric distillation of petroleum : light diesel fraction (LDF, cut 453-513 K), hydrogenate (HG, cut 513-633 K) and denormalizate (DN, cut 473-573 K). The latter is obtained after hydropurification and isolation of the n-paraffin hydrocarbons (Parex process). We have also used a source for the production of normal paraffins (NP) and a heavy diesel fraction. Our investigations on the formation of total insolubles in diesel fuels were based on ASTM D 2274-8019.

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Chemical stability of diesel fuels: Zh. 0. Kalitchin et al.

Table 1 Components and physico-chemical characteristics of the samples Components DN HG LDF NP Characteristics Density at 20C Fr(agctZaY )content boiling point (C) 10% 50% 90% End of boiling (C) Kinematic viscosity at 20C (mm2 s-i) Sulphur (mass % ) Mercaptan sulphur (%) Ash (%) Corrosion on copper plate Water soluble acids Acidity (mg KOH per 100 ml) Resins (mgper lOOmI) +, Stable 100 100 20 20 80 80 80 20 80 10 20 30 40 Content (vol %) 90 70 60 90 10 70 30 60 40

0.832

0.820

0.832

0.832

0.821

0.823

0.832

0.832

0.828

0.821

0.821

0.822

196 218 248 280 300 3.4 0.04

185 215 248 281 300 3.3 0.03

178 212 246 281 298 3.3 0.15 0.0048 _

188 216 246 280 304 3.4 0.23 0.0052

185 215 247 283 300 3.2 0.14 0.0052 -

188 214 251 283 301 3.3 0.22 0.0050

180 216 247 280 301 3.4 0.09 0.0028

176 213 251 283 301 3.3 0.18 0.0080

183 209 247 286 301 3.1 0.26 0.0101 _

185 214 247 283 302 3.3 0.09 0.0032

185 211 249 284 305 3.2 0.19 0.0074

179 215 247 284 306 3.1 0.26 0.0100 -

+ -

+ -

+ _ 0.17

+ 0.17 -

+ _
0.17 -

+ _
0.23 _

+ 0.11 _

+ 0.23 -

+ _
0.35 -

+ 0.11 -

+ 0.23 _

+ _
0.35 _

Table 2

Results of the studies according to ASTM D 2274-80 modified for the experiment in the kinetic region at 368 K Colour (ASTM-1500) Non-oxid. 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 3 Oxidized 2 2 2 2 2.5 2.5 1.5 2 2 2 2 2 2 2 2 2 4

No 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17

Sample 10% LDF + 90% HG 20% LDF + 80% HG 30% LDF + 70% HG 40% LDF + 60% HG HG DN 10% LDF + 90% DN 20% LDF + 80% DN 30% LDF + 70% DN 40% LDF + 60% DN 20% LDF + 80% DN + additive I 20% LDF + 80% DN + additive II 20% LDF + 80% DN + additive III 20% LDF + 80% DN + ADM 15-1 20% SNP + 80% DN 20% SNP + 80% HG Heavy diesel fraction

[ROOH], (mol I-) (x 103)

0
0 0

(Acid no.), (mg KOH per 100 ml)

0 0 0 0

(Acid no.), (mg KOH per 100 ml)

0
0

Total insolubles (mg per 100 ml) 0.60 0.30 0.50 1.24 6.90 4.33 0.62 0.58 1.22 1.27 0.22 0.54 0.54 0.34 0.93 0.67 1.62

0
0

26 46 0 0 0 0 0 0 0 0 0 0 0

0 0 0 0 0 0 0 0 0 0 0 0 1.3

0
0

0 0 0 0
0

0
0

0
0 0

7.4

*[ROOH],

and (acid no.), are determined after 16 h of accelerated ageing

According to the standard the oxidation is carried out at 368 K with an oxygen flow rate of 5 1 h-i. Our results obtained at 368 and 413 K with additional stirring of the reactors (60 rev min- ), and an oxygen flow rate of 14 1 h-i, showed that more information about the stability of the samples is given at the higher temperature (Tables 2 and 3). We used a modified apparatus where accelerated ageing of six samples was carried out simultaneously. The temperature change was kept in the

range of + 1 K. In order to have conditions for the process to occur in the kinetic region and to prevent sedimentation of the solid phase, the thermostatically controlled part of the apparatus was attached to a stirring mechanism. The construction of the stirring mechanism is given in Ref. 20. For a more precise and uninterrupted study of the formation of total insolubles we used a nephelometric method in parallel to the gravimetric measurements.

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Table 3 Results of the studies for samples of diesel fuel at 413 K

of diesel fuels: Zh. D. Kalitchin et al.

Total insolubles No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 Sample 10% LDF + 90% HG 20% LDF + 80% HG 30% LDF + 70% HG 40% LDF + 60% HF HG DN 10% LDF + 90% DN 20% LDF + 80% DN 30% LDF + 70% DN 40% LDF + 60% DN 20% LDF + 80% DN + additive 20% LDF + 80% DN + additive 20% LDF + 80% DN + additive 20% LDF + 80% DN + ADM 20% SNP + 80% DN 20% SNP + 80% HG Heavy diesel fraction of hydroperoxides I II III 15-I (mg per 100 ml) 9.60 4.30 5.21 12.68 2321.00 833.03 39.79 6.79 15.20 16.06 7.18 33.91 2.84 15.64 31.50 10.60 36.47

(Acid no.), (mg KOH per lOOmI)

Maximum light scattering (%) -____575 nm 600 nm 160 30 38 155 5000 2400 155 50 170 175 84 134 19 59 280 163 285 ~40 II 6 71 2900 1450 59 8 70 65 8 82 6 22 125 125 126

Maximum light scattering (%) --_____~ 575 nm 600 nm 0 0 11 4 0 0 12 4 0 6 0 3 0 0 0 0 0 error 0 0 3 4 0 0 4 0 0 4 0 0 0 0 0 0 0

Total insolubles under Ar (mg per 100 ml) _ 0.70

Induction period of total insolubles formation (h) 1.5 0 0.5

0 0 0 0 836 306 0 0 0 0 6.1 0 0 0 0 0 48.2

0.37

0 2.5

_. _ 0.38 _

3.0 1.5 0 0 1.2

_ ._ _

12.0 0 5.5 0 0

0 0

The concentration

in the samples is zero within the limits of experimental

350

400

450 A

500

550

600

(nm)

Figure I Spectral distribution of the intensity of the scattered light for sample containing 20% LDF and 80% HG and its change with time: 0, at the beginning of the experiment; 0, after 3.5 h; A, after 6h;A,after9h;n,afterl2h;m,after16h

This enabled us to make a quantitative assessment of the presence of a heterogeneous phase in the oxidized diesel fuels. In order to exclude the possibility of mixing in the spectra from light scattering and fluorescence, due to the presence of compounds with condensed nuclei2, we studied the fluorescence spectra of the initial samples. These spectra showed that no fluorescence is observed in the region from 350 to 800 nm on irradiation in the U.V. region. The fluorescence spectra of the oxidized samples (after the total insolubles were filtered) showed two weak maxima at 385 and 468 nm, respectively. The wavelength of the irradiation light in this case was 350 nm. Hence the observed increase in the region 500-800 nm (see Figure 1) is due only to light scattering. The nephelometric measurements were carried out on apparatus which enabled us to measure the intensity of the light flux perpendicular to that coming from the light

sources, in the visible region, at the same wavelength. Figure 1 gives the spectral distribution of the intensity of the scattered light for a sample containing 20% LDF and 80% HG and its dependence on time. Similar relationships are observed for the other samples. The experiments were carried out in conditions of accelerated ageing at 413 K in an oxygen atmosphere. As can be seen from Figure 1 the intensity of the scattered light in the region from 500 to 700 nm increases with time. The reason for the decrease in intensity of the light at 350-500 nm is the formation of compounds as a result of oxidation, which absorb in this spectral region. Gravimetric measurements were carried out after the samples subjected to accelerated ageing were filtered through Schott-filter 4G, under vacuum, according to Ref. 19. In order to use the results obtained by the nephelometric method for evaluating the formation of solid phase in the sample we studied the correlation between the amount of total insolubles determined gravimetrically and the intensity of the scattered light at 575 nm. Figure 2 shows that good correlation is obtained between those two parameters. For samples HG and DN (5 and 6 in Table 3) a plateau is observed in the nephelometric kinetic curve after 16 h. This is most probably due to the fact that the total insolubles particles formed are too big and sedimentation takes place due to cohesion of particles. In our studies we used nephelometric kinetic curves in the time interval 0- 16 h, where there is a good correlation with the gravimetric results. The decrease in the measured intensity of the scattered light after the filtration by more than 20-fold (Table 3) is additional proof that the intensity of the scattered light is due to the heterogeneous phase formed. The amount of total insolubles determined at the end of the accelerated ageing for 16 h at 413 K corresponds to the measured maximum of the light scattering reflection determined for the same samples (Table 3).

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200

5.0 Time [h)

10.0

15.0

Figure 2 Dependence of the scattered light (0 ) and the total insolubles ( l ) on time for a sample containing 20% LDF and 80% DN at 413 K

RESULTS AND DISCUSSION The most important parameter in determining the chemical stability of diesel fuels is their stability towards formation of total insolubles. Stringent demands involving this parameter under the conditions of accelerated ageing at 368 K are stipulated in USA and USSR standards,19. Comparison of the conditions given in ASTM D 2274-8019 and the considerations given in Ref. 23 shows that the oxidation in the former is not in the kinetic region, because of the low gas flow rate and the sedimentation of the total insolubles because of lack of stirring. In order to distinguish the chemical stability of the diesel fuels the accelerated ageing experiments should be carried out in the kinetic region. The results of the comparative studies of different model diesel fuels and fractions at 368 K are given in Table 2. The initial samples do not contain hydroperoxides according to the method described in Ref. 24. The same applies to the samples subjected to 16 h of accelerated ageing in an oxygen atmosphere. It has been reported in the literaturez5 that samples HG and DN contain a small amount of sulphur (Table I ). Sulphur compounds in the samples are in the form of organic compounds (sulphides, thiophenes, thiophanes, etc.) which decompose hydroperoxides26. The latter are found in large amounts in samples 5 and 6 (HG and DN), where the sulphur content is insignificant. This result shows that the samples are not an exception to the other light fuels with the oxidation proceeding by a radical chain mechanism with degenerate chain branching. Both the initial samples and those after oxidation under the same experimental conditions do not contain acids*. Taking into account the above concerning the oxidation mechanism there should be acids formed. Obviously, the acids are rapidly consumed during the formation of total insolubles. The data in Table 2 show that a temperature of 368 K does not enable any distinction to be made between the samples with respect to their ability to form total insolubles. The same applies to the influence of additives. This is confirmed by the data in Table 2 for samples where the HG and DN contents are changing (samples l-4 and 7-10). The differences between the experimental data in these cases are in the region of experimental error. In order to achieve an improved differentiation in the thermo-oxidative and thermal formation stages of total insolubles and to take into account the factors influencing the chemical and

oxidative stability of diesel fuels, the samples listed in Table 2 were studied in the same apparatus, but at elevated temperature (4 13 K ). The amount of total insolubles was determined gravimetrically at the end of the experiment and at maximum light scattering. The results show that there exists a dependence between the amount of total insolubles and the sulphur content ; a sharp minimum is shown in Figure 3. Sharp differences are observed between HG and DN and the other samples with respect to the total insolubles formed at the end of the accelerated ageing. Taking into account these results we carried out our studies at 413 K and we recommend this temperature as being the more appropriate for studying total insolubles formation in accelerated ageing. It can be seen that hydroperoxides are not formed at elevated temperatures. The kinetic studies of hydroperoxides formation showed that maximum production is reached 6 h after the beginning of the oxidation, after which their decomposition rate is greater than the overall rate of formation (Figure 4). As can be seen from the data in Table 3 for most of the samples at 413 K the formation of organic acids is not observed. The exceptions are samples 5, 6 and 17, where a dramatic rise in the acid number is observed. Comparing these results for the first two samples (DN and HG) with the results of total insolubles formation, then these acids can be regarded as precursors of the total insolubles. Obviously, the presence of a moderate amount of sulphur (0.09-0.36 mass %) suppresses the formation of carboxylic acids and of total insolubles. We studied whether total insolubles formation is due to oxidation reactions or whether they can form in an anaerobic atmosphere. For this purpose some of the samples were subjected to accelerated ageing at 413 K for 30 h under an argon atmosphere (Table 3). The amount of the total insolubles formed is less than in an

t
40.0 = E 8 i P B I) 3 sl .t m ;; + 10.0 30.0 -

20.0

.i

0.1

0.2 Sulphur content

0.3 (mass 8)

0.4

Figure 3 Dependence of the total insolubles after 16 h on the sulphur content for samples containing different amounts of DN (0) and HG (0 ) at 413 K. The values on the abscissa are taken from Table I for different blends where the amount of DN and HG varies from 60 to 100 vol%

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7000

00

3.0

6.0

9.0 Time(h)

12.0

16.0

Figure 4 Dependence of the concentration of hydroperoxides and acid on time for: DN - 0, hydroperoxides, 0, acids; HG - 0, hydroperoxides, n , acids

oxygen atmosphere after 16 h. We tested three samples (2, 4 and 8) which are the most stable towards total insolubles formation in an oxygen atmosphere. These data confirm the existence of two processes: thermal reactions and reactions influenced by oxygen. The amount of total insolubles formed under an argon atmosphere is only 16% of that formed in an oxygen atmosphere for sample 2. In the literature 1o-13,17 it is stated that the formation of total insolubles can be considered as a polymer chain reaction. We can express the oxidation rate in an oxygen atmosphere by the following equation :
Wp, = k;

CWg~~~W/Jk,

(1)

where c is the maximum rate of total insolubles formation in an oxygen atmosphere, k: is the rate constant of chain propagation, [M] is the concentration of monomer in the diesel fuel, [0,] is the oxygen concentration in the sample, ko is the rate constant of chain initiation and k, is the rate constant of chain termination. The equation for the rate of total insolubles formation in an argon atmosphere is :

constant of initiation. However, according to Equation (2), [M] - l/,,@, if the total insolubles formation is due only to a polymerization process. Therefore, the formation of total insolubles is not just a polymerization reaction in diesel fuels. The influence of sulphur content on the stability of diesel fuels was also studied. The dependence of the isolated total insolubles on the sulphur content is given in Figure 3. A sharp minimum is observed at a sulphur content of 0.1 mass%. With LDF, with a sulphur content of 0.36 mass% the formation of total insolubles is suppressed. Our experimental data show that the optimal concentration of LDF in a model diesel fuel is 20 ~01% with respect to the formation of total insolubles (samples 2 and 8 in Table 3). Up to a concentration of 0.3 mass% the sulphur compounds inhibit the formation of total insolubles. Their increase leads to the formation of insoluble compounds due to reactions with the organic bases in the model diesel fuels. It should be noted that no additional sulphur compounds are doped in the sample, and the plot in Figure 3 is made by expressing the amount of total insolubles versus the sulphur content in the samples (Table 1). The temperature of 413 K enabled us to study the ability of several additives to inhibit the formation of total insolubles (Table 3). We have studied the commercially available additives I, II, III and ADM 15-I. (ADM 15-I represents a mixture of metal deactivator (Schiff base) and free radical acceptor inhibitor.) The experimental data in Tables 2 and 3 show that due to the presence of a natural sulphur containing inhibitor in the diesel fuels the additives do not have a significant inhibiting effect on total insolubles formation at 368 K (Table 2) and 413 K (Table 3). By choosing components with different sulphur contents and by analysis of the kinetic data one can obtain diesel fuels stable with respect to the formation of total insolubles. This is illustrated in
Figure 3.

(2)
where Wi is the maximum rate of total insolubles formation in an argon atmosphere, ki is the rate constant of chain propagation and kT is the rate constant of chain initiation. If it is taken into account that the rate constants k, and k, in Equations (1) and (2) have the same value, for the ratio of the rates of total insolubles formation the following equation is obtained :
g = Jmco,lIJm

The nephelometric method developed by us to follow the kinetics of formation of total insolubles gave us the opportunity to determine the induction period of this process (Table 3). No induction periods are observed for samples 2, 3, 8, 9, 11, 14, 15, 16 and 17 (Table 3). Relatively high values are observed for samples HG and DN, although the rate of formation of total insolubles is an order of magnitude greater for the rest of the samples. Additives I and III cause relatively high induction periods and lead to small amounts of total insolubles after 16 h of accelerated ageing at 413 K. The induction period is not a reliable parameter for predicting the stability of diesel fuels with respect to the formation of total insolubles.

(3)

CONCLUSIONS 1. A new method is developed for following the kinetics of formation of total insolubles in diesel fuels using light scattering on the basis of nephelometry. 2. Twenty-two samples of model diesel fuels are analysed with respect to their chemical stability. They include denormalizate, hydrogenate and four mixtures of both components with a light diesel fraction and a source for normal paraffins. 3. By comparing experimental data with values of the initiation rate constant for total insolubles formation

Our experiments showed that the left-hand side of the equation has a value of 6.25 for sample 2 (Table 3) (see above). If we substitute the oxygen concentrationi in the sample (7.8 x 10m3 mol 1-l) for the concentration of the monomer we obtain the following expression: [M] = a/k (4)

where a has a value of 1.4 x 10m4 s. Obviously, according to Equation (4) the concentration of the monomer is inversely proportional to the rate

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of diesel fuels: Zh. D. Kalitchin

et al.
9 10 11 12 13 14 15 16 17 18 19 20 Roel, R. J. Inst. Petr. 1964, SO, 22 Skepfer, M. W. Oil Gas J. 1984,52, 79 Taylor, W. and Frankfield, J. Ind. Eng. Chem., Prod. Res. Dev. 1978, 17,86 Taylor, W. Ind. Eng. Chem., Prod. Res. Dev. 1976, 15, 64 Schwartz, F. and Whisman, M. Mines Bull. 1972, 660, 58 Schwartz, F. and Whisman, M. Mines Bull. 1964, 662, 44 Kalitchin, Zh. D. PhD Thesis IOC BAS, Bulgaria, 1988 Li. F. and Li. N. Fuel 1985. 64. 1041. 1047 Ritchie, J. J. inst. Petr. 196j, gl, 298 Kalitchin, Zh. D., Ivanov, Sl. K., Tanielyan, S. K. et al. Fuel submitted ASTM D 2274-80, Sofia, 1983 Ivanov, Sl. K., Tanielyan, S. K. and Tzonkovski, I. M. Khim. Ind. 1985, 27, 13 (in Bulgarian) Kalitchin, Zh. D., Schmulovitch, V., Ivanov, S. K. et al. Dokl. AN SSSR 1986,290, 880 Calvert, J. and Pitts, J. Photochemistry, Mir, 1968, p. 238 Schmulovitch, V. G. and Goldenberg, V. I. Nefekhimia 1972, 19,912 Uvanov, S. K. and Kateva, J. Compt. Rend. Acad. Bulg. Sci. 1968, 21, 681 Kanariev, K., Ivanov, At. and Kutzarova, Z. Khim. Znd. 1986, 58, 346 Ivanov, S. K. in Developments in Polymer Stabilization - III, Applied Science, 1982, p. 55 Bulgarian State Standard BDS 14369-77, Sofia, 1983

calculated by the kinetic approach it is shown that this process is not just a polymerization reaction. 4. The sulphur content in diesel fuels up to a concentration of 0.3 mass% inhibits total insolubles formation. By choosing components with different sulphur contents and on the basis of kinetic data, diesel fuels stable towards the formation of total insolubles can be formulated more successfully than by using some conventional additives.

REFERENCES
1 2 3 4 5 6 7 8 Gureev, A. A., Seregin, E. P. and Azev, V. S. Qualification for Petrol Fuels, Khimia, Moscow, 1984, p. 104 (in Russian) Voorhees, V. and Eiseinger, J. J. Sot. Auto. Eng. 1929,24,584 Mardles, T. and Ross, C. J. Inst. Pew. Technol. 1929, 15, 657 Wagner, C. and Human, J. Oil Gas J. 1929, 12 Brooks, B. Ind. Eng. Chem. 1929, 18, 1198 Flood, D., Hladky, J. and Edgar, A. Ind. Eng. Chem. 1933,25, 1234 Martin, S., Grull, W. and Lowy, A. Ind. Eng. Chem 1933,25,381 Morrell, J., Dryer, C., Lowry, G. et al. Ind. Eng. Chem. 1934, 26,497, 885

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