LITERATURE CITED i. 2. 3. 4. 5. 6. 7. S . N . Khadzieva (ed.), Cracking Petroleum Cuts on Zeolite-Containing Catalysts [in Russian], Khimiya, Moscow (1982).

"Cat cracker operations focus on feed qualities," Oil Gas J., 80, No. 8, 129-139 (1982). U . S . Patent No. 3,685,959. "Octane boosted by special catalyst mechanisms," Oil Gas J., 84, No. 41, 55-60 (1986). J . J . Lipinski and J. R. Wilcox, Oil Gas J., 84, No. 47, 80-82 (1986). L. ~. Kruglova, S. N. Khadzhiev, S. L. Andreev, et al., Khim. Tekhnol. Topliv Masel, No. I0, ii (1991). L. ~. Kruglova, S. N. Khadzhiev, Z. I. Syunyaev, et al., Khim. Tekhnol. Topliv Masel, No. 2, 5-7 (1987).

DETERMINATION OF THE COMPOSITION OF WORKING MOTOR OILS BY CHROMATOGRAPHY AND SPECTROSCOPY V. A. Zakupra, V. D. Reznikov, V. V. Poletukha, and A. G. Pavlov UDC 665.765-404:621.892.096

A technique of liquid column chromatography (LCC) for separation of used oil followed by analysis of the separated groups of compounds by IR spectroscopy has been tested on a model oil containing only a detergent and on a commercial oil of group B with low additive content [i]. The goal of the present work was a further study of the change of composition of oils in the process of aging in the engine and also an improvement of the research technique. Two oils of group D with high additive content were tested; these are provisionally designated A and B. Oil A is a thickened motor-transmission-hydraulic oil for industrial tractors (type STOU, class SAE 10W-30), while oil B is unthickened diesel oil for moderatespeed marine and locomotive engines operating on low-sulfur diesel fuel. The basic physicochemical characteristics of these oils are given in Table i. Both oils were tested by the IM-144S method [i, 2] on an IM-I single-cylinder machine operating on fuels with 1 wt. % sulfur content. The results of fouling of pistons after each test cycle are given in Table 2. As can be seen, oil B is less subject to aging: the TABLE 1 Oil Characteristic A Viscosity at IO0~ Viscosity index Ash, sulfate, %
Alkali

TABLE 2 Fouling of piston, points Overall evaluation, points

B 14,7 99 1,7 12,1

270 -14 Oil A 0-48 48-96 96-144 Oil B 0-48 48-96 96-144

o aJ

mm2/sec

n u m b e r , kg KOH/g

9,95 121 1,,t 9,1 210

Test cycle (GOST 20303-74 ), h

=>o
0 "~

o~Z
~.~

Temperature, ~ flash point pour point

.42

0 0,5 3,5
0 0 0

8,0 9,0 11,7

7,0 9,0 10,0

0 0,4 1,0
0,I 0,1 0,2

8,0 9,4 12,7

7,1 9,1 10,2

0,2 0,5 2,2

1,1 3,3 3,7

8,2 10,4 18,4

8,2 12,4 13,9

MASMA Scientific-Production Association; All-Union Scientific Research Institute of the Petroleum Industry. Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 12, pp. 27-30, December, 1991. 0009-3092/91/ii12-0679812.50 9 1992 Plenum Publishing Corporation 679

TABLE 3 Composition of sediment, wt. %

C

Composition of products of LCC separation of oil after removal of sediment, wt. % NHAA (from column I)
r" = O O O O O ~ O O O O ~

Status

.Q C 0 0

losses

n0of aromatic
hydrocarbons (frOm column 4)

of oil

01,~

Oil A
Starting After operation for, h 24 48 72 96 120 144 0,35 67,87 75,42 83,16 83,91 84,04 83,3 2,27 1,91 2,07 1,91 1,99 1,94 28,9 17,8 9,8 8,2 8,5 8,8 54,5 53,5 54,8 50,7 49,1 48,1 45,0 6,9 6,8 6,7 8,4 9,6 9,1 10,5 32,5 33,2 33,4 33,2 34,4 36,5 36,8 6,1 6,5 5,1 7,7 6,9 6,3 7,7 1,5100 1,5150 1,5180 1,5410 1,5450 1,5470 1,5520

0~4
1,2 2,1 3,0 5,4 . 8,0

Oil B Starting After operation for, h

24 48 72 96 120 144

0
0,3 1,0 1,85 3,5 8,I 7,9

76,13 82,42 80,70 83,05 82,23 82,18

2,87 2,34 2,50 2,39 2,23 2,31

15,0 11,8 i 1,6 12,6 13,5 12,1

54.5
56,7 57,6 54,4 53,6 53,0 55,0

6.2
6,3 6,2 7,5 8,8 8,6 9,4

83,2
32,4 29,4 29,2 31,7 32,4 32,4

6,1
4,6 6,8 8,9 5,9 6,0 3,2

1,51 i0
1,5130 1,5150 1,5390 1,5400 1,5410 1,5490

Notes. i) Data given are average results of two to three determinations. in LCC separation include irreversibly adsorbed compounds.

2) Losses

increase of fouling of the piston is comparatively less and the piston rings remain completely free to move (0 points up to the end of the test). Samples of the motor oils (starting oils and after various periods of operation) were dissolved in benzene, centrifuged to remove sediment [i], and after driving off the benzene were subjected to LCC separation in the four-column system developed for analysis of oil fractions [3]. However, in contrast to the technique of [3], column 2 was packed with a 0.2-0.08 mm fraction of ASKG silica gel that had been treated beforehand (HCI and HzO 2) and activated (6 h at 160~ while columns 3 and 4 contained the same fraction of ASM silica gel, had been created in the same way. Replacing aluminum oxide with silica gels that are less active with regard to the initiation of side chemical reactions (during chromatographic separation) was due to the need for further study of the separated groups of compounds. The weight of the sample used for LCC separation was 0.4-0.6 g. The nonhydrocarbon compounds, additives, and aging products collected from column 1 (we will symbolize them as NHAA) were subjected to a second LCC separation in a vertical glass column with descending flow [4]. The columns were packed to a height of 600 mm with ASKG silica gel, to which 70 wt. % water was added after activation and cooling. A weighed amount of the sample (about 0.i g) was thoroughly mixed with i ml of this same silica gel and transferred quantitatively to the column. Elution was done in succession with n-hexane (3 ml), benzene (1.5 ml), chloroform (2 ml), mixtures of chloroform with acetone in ratios of 3:1 (1.5 ml), 2:1 (1.5 ml), i:I (i ml), acetone (i ml), and 96% ethanol until the sample was completely displaced from the column. The volume rate of collection of eluate was 20-25 drops per min. These chromatography conditions, which were determined on model mixtures of various oil additives, assure separation with respect to increasing polarity from the aromatic hydro-

680

A l
E" ~ I I

Fig. i. Chromatograms of repeat LCC separation of NHAA groups from oil A (m, mass of substance; n, number of eluate fraction - 40 drops): a) starting oil; b) after 144-h operation; 1-4) peak numbers.

carbons in the oil up to sulfonate additives displaced from the column by ethanol. The concentration of cirbon and hydrogen in the sediments after centrifuging was determined by the technique of Korshun and Gelman; the concentration of noncombustible residue was determined by weighing after burning the weighed sample in the determination of carbon and hydrogen [5]. IR spectra were recorded in thin layer without solvent on a UR-20. Table 3 shows the change of composition of both motor oils in the process of testing. The investigation of this change using the indicated techniques, which is more detailed than in [i], makes it possible to evaluate the individual components of the oils with respect to their behavior in operation. As can be seen, the yield of sediment, which consists principally of soot, wear products, and inorganic salts [6], increases with time of operation for both the oils in approximately the same way. The particles of sediment here become carbonified (the concentration of carbon increases and the concentration of hydrogen decreases). For both oils the concentration of noncombustible residue in the sediments at first decreases noticeably with use, and then stabilizes at approximately the same level. Judging from the element composition and amount of noncombustible residue, mainly carboniferous particles (soot from incomplete combustion of diesel fuel [6]) accumulate in the oil during use. The large amount of noncombustible residue in oil A after 24 and 48 h and in oil B after 24 h is due to the passage of calcium carbonate or hydroxide from the alkali additives, which was still present at this time, into the sediment. The LCC separation of the motor oil samples produced chromatograms, each of which has three distinctly separated peaks, which characterize the paraffinic-naphthenic hydrocarbons (from column 4), aromatic hydrocarbons (from column 4), and NHAA (from column i); see Table 3. in use the concentration of paraffinic-naphthenic hydrocarbons in oil B does not change, while in oil A it decreases by ~i0 wt. %. An increase of the refractive index nD z~ of the aromatic hydrocarbons is characteristic for both oils with increasing time of operation in the engine, which is evidence of a change of composition of these hydrocarbons. However, their total composition changes little. The concentration of NHAA in both oils increases approximately the same: by 3.6 wt. % in oil A and by 3.2 wt. % in oil B. The changes of the hydrocarbon part of oils A and B are in agreement with the description of their bases - respectively light and viscous distillates of narrow fractional composition (see Table i). Repeat LCC separation of the NHAA separated from both of the tested oils produced chromatograms with four clearly separated main peaks (Fig. i). From the IR spectra the substance corresponding to peak 1 consists of aromatic hydrocarbons (their appearance is due to degradation of the separation power of column 1 because of the increase of weight of the sample to 1-1.5 g in the last experiments, which were conducted with the goal of obtaining a sufficient weight of NHAA for repeat LCC separation). 681

'a

50(]

700

7100

150(]

].60(]

JO(]O 5400

Waventunber, cm- I

Fig. 2. IR spectra of substances isolated in repeat separation of N I ~ from unused (a) and used (144 h) (b) o i l A and corresponding to peaks 2 (curve T), 3 (curve I f ) , and 4 (curve I I I ) .
The IR spectra of the substances isolated from the NHAA of the starting oil A and corresponding to peaks 2-4 exhibit characteristic absorption bands that allow them to be attributed to the following additives (Fig. 2): dialkyl dithiophosphates (peaks 2 and 3) - the bands at 670 and i010 cm -I (stretching vibrations of P=S and P-O-Calky I bonds, respectively) [7-9]; polymethacrylates (peaks 2 and 3) - the band at 1740 cm -I (stretching vibrations of C=O bond of aliphatic ester; this band appears in the form of a shoulder in the spectrum of peak 3) [i0, 11]; alkyl salicylate detergent (peaks 2 and 3) in the form of alkylsalicylic acid, which is obtained as a result of ion exchange on silica gel in the process of chromatography [12] - bands in the region of 1670 cm -I (in spectrum I, in the form of a shoulder) and 2500 and 3400 cm -I (stretching vibrations of C=O bonds and the O-H of the carboxyl group [13]); sulfonate detergent (peak 4) - bands at 1070 and 1200 cm -I (symmetric and asymmetric stretching vibrations of S=O bond, respectively) [i0, 14, 15]. After 96 h of operation of oil A the IR spectra of the substances extracted from the NHAA and corresponding to peaks 2 and 3 show a significant decrease in the intensity of the bands of the dialkyl dithiophosphates (670 and i010 cm -l) and an increase of the intensity of the band at 1710-1720 cm -l (oxidation products) with respect to the band at ~1470 cm -l [I0], which is characteristic for bending vibrations of CH 2 and CH 3 groups (this band was taken as an internal standard). After 144 h of operation the IR spectrum of the substance corresponding to peak 3 (see Fig. 2b) practically does not contain the bands characterizing dialkyl dithiophosphate and the alkyl salicylate detergent (1670 cm-1). However, these bands are nevertheless seen in the spectrum of the substance corresponding to peak 2. The spectra of the substances corresponding to peaks 2 and 4 retain the absorption bands of polymethyl methacrylate (1740 cm -I) and the sulfonate detergent (1070 and 1200 cm-1). There is a further increase of the intensity of the band at 1710-1720 cm -l (oxidation products). Thus, in oil A after 144 h of use there is significant depletion of the dialkyl di-

682

thiophosphates (principally the more polar molecules of the substance corresponding to peak 3, which are strongly held in the chromatographic column) and of the alkyl salicylate detergent and to a lesser degree of the polymethyl methacrylate and sulfonate detergent. At the same time there is accumulation of oxidation products. The IR spectra of the substances isolated from the NHAA of oil B and corresponding to peaks 2-4 exhibit characteristic absorption bands allowing them to be attributed to additives of alkylphenol type (basically in the substance corresponding to peak 2 and in part peak 3) - bands of aromatic structures (830, 1490, 1520, 1600, 3000-3100 cm-1), phenol hydroxyl (3620 cm "l in the form of a shoulder on the intensity of the broad band of the H-bond-perturbed OH groups with maximum absorption around 3420 cm -l) [i0], and to the sulfonate detergent (the substance of peak 4) - bands at 1070 and 1200 cm -l (their attribution is given above). After 96 h operation of oil B the IR spectra of the substances isolated from the NHAA and corresponding to peaks 2 and 3 exhibit a redistribution of intensities of the absorption bands of aromatic structures and carbonyl-containing compounds (around 1710 cm -I) in the direction of the latter, which is evidence of partial depletion of the alkylphenol additive and accumulation of oxidation products. From the IR spectra of the substances of peaks 2 and 3 after 144 h operation of oil B one can see that there is further depletion of the alkylphenol additive and accumulation of oxidation products. The spectrum of the substance corresponding to peak 4 still shows the sulfonate detergent. Thus, based on the change of composition of oils A and B during use, in particular the results of comparing the depletion of the additives and accumulation of oxidation products, one can conclude that oil B is more resistant to aging. The deeper aging of oil A results in the greater fouling of the piston of the IM-I unit in the third test cycle (96-144 h) and a partial loss of freedom of the piston rings. This technique of differential chromatographic separation of nonhydrocarbon compounds, additives and aging products according to their polarity followed by IR spectral analysis permits more complete investigation and monitoring of the depletion of individual additives (over their components) and the accumulation of oxidation products and, in the final account more objective evaluation of the time of active operation of the individual components of a motor oil and its useful life overall. LITERATURE CITED i. 2. V. A. Zakupra, V. D. Reznikov, and P. M. Krylina, Khim. Tekhnol. Topl. Masel, No. i, 26-29 (1988). F. N. Merzlikin, V. D. Reznikov, E. N. Shipulina, et al., Tr. VNII NP, No. 25, 31-39 (1977). V. A. Zakupra, P. M. K r y l i n a , V. I . R y b a l k i n , et a l . , Khim. Tekhnol. Top1. Masel, No. 9, 35-38 (1988). V. A. Zakupra and T. I . Chernetskas, Khim. Tekhnol. Top1. Masel, No. 6, 51-55 (1973). V. A. Klimova, Basic Micromethods of A n a l y s i s of Organic Compounds [ i n R u s s i a n ] , Khimi y a , Moscow (1967). V. D. Reznikov and ~. N. S h i p u l i n a , Khim. Tekhnol. T o p l i v Masel, No. 9, 24-29 (1989). A. B. V i p p e r , V. N. Bauman, K. A. Egorova, et a l . , Khim. Tekhnol. T o p l i v Masel, No. 6, 47-50 (1971). S. Surban, Revue (De l ' I n s t i t u t F r a n c a i s du P e t r o l ) , 40, No. 2, 251-264 (1985). K. A. Egorova and V. N. Bauman, N e f t e p e r e r a b . Neftekhim. ( K i e v ) , No. 11, 10-14 (1974). K. Nakanisi, Infrared Spectra and the Structure of Organic Compounds, A. A. Meltsev (ed.) [Russian translation], Mir, Moscow (1965). G. G. Kotova, N. S. Sosina, and K. I. Zilina, Tr. VNII NP, No. 14, 234-240 (1976). V. A. Zakupra and S. V. Timoshenko, Khim. Tekhnol. Topl. Masel, No. 2, 48-52 (1980). V. A. Zakupra, S. V. Timoshenko, Yu. T. Gordash, et al., Khim. Tekhnol. Topl. Masel, No. 5, 57-60 (1976). G. G. Kotova and K. I. Zimina, Khim. Tekhnol. Topl. Masel, No. 3, 31-33 (1973). G. G. Kotova, N. S. Sosina, K. I. Zimina, et al., Tr. VNII NP, No. 12, 267-274 (1970).

3. 4. 5. 6. 7. 8. 9. i0.
ii. 12. 13. 14. 15.

683