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CHEMICAL COMPOSITION OF USED M O T O R OILS

V, A. L i t v i s h k o v a , A. I. B u k h t e r , U D C 665.521.5
A. V N e p o g o d ' e v , a n d A. M. B e z h a n i d z e

Changes in oil composition during engine operation are caused by the accumulation of solid contaminants
and by chemical conversion of the additives and the hydrocarbon base oil. For many years it was assumed that the
chemical composition of the base oil remains essentially unchanged during operation and that the quality and prop-
erlies of additive-free oils can be completely restored by treatment to remove contaminants [1]. Some investiga-
tors have held the opposite opinion that the chemical composition of the oil undergoes considerable change during
operation in an engine [2].
The need for a more critical study of changes in hydrocarbon base oils is dictated by the increasingly severe
requirements placed on oil quality.
Here we are presenting results from a study of four used-oil samples:
(1) DS-11 without additives, used 40 h in an IKM-1 single-cylinder carburetor-engine unit;
(2) AS-8 containing 3.5~ VNII NP-360 additive [barium alkylphenolate and zinc bis(alkylphenyl)dithiophos"
phate] after a 5000-kin test run in a Volga automobile;
(3) AS-8 consisting of the distillate fraction recovered from used oil (sample 2) by vacuum distillation, plus
16% freshresidual component, this blend having been operated 40 h in an IKM-1 unit;
(4) mixture of used diesel oils after reclaiming.

TABLE I. Composition of New and Used Oils


Hydrocarbon group content (in %)
paraf- aromatic t total residue oi
Oil yield in silica gel
finic-- group group group resins separa- and losses
naph-
thenic I II III Ilion

Mixture of used diesel oils after reclaiming 66, 7 13,0 2,8 8,4 9 5,3 96,2 3,8
Reclaimed
98070H~SOa(3% by weight). 69,0 13,9 5,0 8,8 3,1 100,0 0,0
20~ N-a2co~ (5%'by.weight) 62,7 13,4 3,2 8,2 3,4 90,6 9,4
DS-11 (i~ditlve-free)
new 54, 1 28,0 16,4 None 0,6 99,1 0,9
used (40 b., IKM-1 unit) ..... 47,8 20,8 :9,6 None 14,6 92,8 7,2
AS-8
new (base oil) 58,5 11,9 18,3 9,8 1,5 100 0,0
new plus 3.5% VNII NP-360 additive 9 . 58,3 11,2 18,6 9,9 1,8 99,8 0,2
Used (GAZ-21 engine, 5000 km run) I 47,3 I1,1 16,3 9,7 2,8 87,2 12,8
Reclaimed distillate plus 16% fresh residual
component 56,5 12,2 18,4 10,6 1,9 99,6 0,4
Used (40 h, IKM-1 unit) 48,0 13,0 14,4 11,2 8,1 94,7 9 5,3

Note: No Group IV aromatic compounds were present in any of the oils.


ROZ VNII NP. Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 12, pp. 50-53, December, 1974".

9 19 75 Plenum Publishing Corporation, 227 West 17th Street, New York, N. Y. 10011. No part of this publication may be repro-
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for $15.oo.

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Frequency, cm -1 Frequency, cm "t

Fig. 1 Fig. 2

Fig. 1. Infrared spectra of new and used oil fractions: a) Group I hydrocarbons; b) OroupII; c) Groups III and IV;
d) resins. Oils: 1) new; 2) used in IKM-1 unit; 3) mixture of used diesel oils.

Fig. 2. Infrared spectra of oil fractions (see Fig. 1 for designations a, b, c, d). Oils: 1) new; 2) reclaimed with
sulfuric acid; a) reclaimed with alkali.

The operating conditions for the oil in the single-cylinder IKM-1 unit were quite severe. At the end of the
test (40 h), the oil viscosity usually had increased by 40-70%.

For purposes of comparison, the corresponding new oils were tested: DS-11, AS-8, and AS-8 plns 3.5% VNII
NP-360 additive.

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TABLE 2. Composition of Hydrocarbon Part of New and The used-oil samples were partitioned on
Used Oils Grade ASK silica gel. Insoluble compounds were
Hydrocarbon group first removed by disolving the oil in n-heptane in
content a 1/3 ratio, filtering the solution through "Blue
Ribbon" filter paper, and distilling off the solvent,
.o .,~ aromatic
Oil the oil sample remaining after this treatment being
used for the adsorptive separation. The fractions
ca,
o obtained in the separation were combined on the
basis of refractive index to make up cuts of the fol-
DS-11 (additive-free) lowing hydrocarbon types:
new 55,0 28,4 16,6 None (1) Paraffinic-naphthenic (n}~ < 1.4900)
used (40 h,
IKM-1 unit) (2) Aromatic
N one
AS-8 plus-3%VNII NP-360
additive Group I (n}~ = 1.4900-1.5300)
new 59,5 12,1 18,6 9,8
Group II (n]~ =1.5300-1.5500)
used (GAZ-21 engine,
5000-km run) 56,0 13,1 19,3 11,6 Group III (n]~ = 1.5500-1.5900)
reclaimed distillate plus Group IV (n]~ > 1.5900)
16% fresh residual c o m -
ponent
57,8 12,5 18,0 10,9 (3) Resinous compounds (all hydrocarbons
desorbed by a l c o h o l - benzene mixture). Each separa-
Used (40 h, IKM-1 unit) 55,5 15,0 16,6 12,9
tion was performed twice, or three times if the yield
Note: No Group IV a r o m a n c hydrocarbons were present was less than 92%. The deviations in parallel e x ,
in any of the oils. periments were at most * 1% for the individual
fractions and the total yield.
TABLE 3. Results of Thermal-Oxidative Stability Tests We must note first of all that we were never
on Oils in IKM-1 Unit successful in any of the used-oil experiments in
Increase in viscosi- achieving complete desorption of the products from
ty at 50"C (%) after the silica gel (Table 1). The silica gel remained
Blend composition dark after separation of the used oils. It is still not
2o h 40 h
clear just what this residue is. We established only
Hydrotreated distillate+ fresh that treatment of the used oil with concentrated
residual component 50 70 sulfuric acid removes these products, and treatment
Contact-treated dis~ltate + fresh with sodium carbonate partially converts them to
residual component 56 80
resins.* None the less, these products must be taken
Distillate + hydrotreated residual 55 79
component into account in the balance for the adsorptive se-
Distillate + contact-lreated residual 73 ll0 paration of used oils.
component
In the used oils, particularly those tested in
80 the IKM-1 unit, decreases in resin content were ob-
served, along with decreases in the content of paraf-
finic-napththenic hydrocarbons and in the Groups I
and II aromatic hydrocarbons; the contents of Groups
III and IV aromatic hydrocarbons were essentially
o unchanged. The drops in paraffinic-naphthenic
"~ so ~ ~>...=_...=..x__~ s hydrocarbon content can be explained in part by the
fact that the used oils (in comparison with the fresh
oils) contain such additional components as "un-
desorbed" resins. If the comparison is made on the
30
basis of the hydrocarbon part of the used oil (total
gO I I I of paraffinic- naphthenic and aromatic fractions
1800 1700 taken as 100%), the relative amounts of the groups
Frequency, cm -1 are very close to those for the new oil (Table 2).
Fig. 3. Infrared spectra of reclaimed oils: 1) Fresh; 2)
mixture of components after vacuum distillation; 3) hy- 9As in Russian Original; statement does not agree
drotreated components; 4) components after contact-treat- with data in Table 1 -- Translator.
ing; 5) deasphalted distillation residue.

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Only a slight decrease in the paraffinic-naphthenic part is observed for the used oil, and approximately the same
increase in the Group Iii aromatic hydrocarbons. The total of Groups I and II aromatic hydrocarbons remains es-
sentially unchanged.
The hydrocarbon groups recovered by adsorplion from the new and used oils were examined in an IKS-14
infrared spectrophotometer in the frequency range of 1810-1550 c m "I to detect the presence of oxidation products
and other products of aging (Fig. i). The paraffinic-- naphthenie fractions of the new and used oils are identical
in this range of frequencies. The spectra of the Group I aromatic compounds show slight differences; greater
amounts of carbonyl compounds are observed in the used-oil fractions (1750 cm'l). The spectra of the Group II
aromatic compounds show that the used oil contains m u c h greater quantities of carbonyl compounds (1710 and 1690
cm'~). Also detected were compounds absorbing at 1630-1640 c m -I, possibly organic nitrates or unsaturated com-
pounds [3]o The spectra of the Group III aromatic compounds show that the used oil also contains considerable
amounts of oxidation products and products that absorb in the 1630-1640 c m "I region. The resins of the used oil
contain three times the amount of oxidation products present in the resins of the new oil. Moreover, the used-oil
resins contain compounds absorbing at 1680-1640 c m ' t . The content of oxygen in the aromatic fractions of the
used oil can be estimated by the method of [4]: 0.1% for Group I, 0.2% for Group II, and 0 . 5 9 for Groups llI and IV
aromatic hydrocarbons.
This comparison of the new and used oils shows that the reIative amounts of hydrocarbon groups in the base
oil change only slightly during engine operation, but the composition of the groups may change substantially.
The oxygen-containing compounds are very difficult m remove from the aromatic fractions and resins of
used oiI. Treatment with concentrated sulfuric acid or sodium carbonate does almost nothing (Fig. 2). It will be
seen from the data of Fig. 3 that the oxygen-containing compounds al~0 persist when the used oil is vacuum-distil-
led, remaining in the distillate and residue even after treatment with liquid propane. We were not even successful
in reducing the content of these compounds in the distillation components by contact treatment with bleaching
clay. Complete removal of the oxygen-containing compounds was achieved only by hydrotreating (gage pressure
40 k g f / e m z, temperature a00~ A1-Co-Mo catalyst). Even after such treatment, the aromatic fractions were dis-
tinguished by higher contents of polyeyclic compounds than were observed in the fresh oil.

In order to investigate the effect of oxygen-containing compounds on the properties of oils tested in the IKM-1
unit, blends were prepared from the overhead and residual products obtained by vacuum distillation of the used oil,
after hydrotreating or contact-treating, with a Group "V" additive package in each of the blends. The blend had a
viscosity of 1t eST at 100~ The test result showed that the oils containing components that had not been treated
to remove oxygen-containing compounds were poorer in thermal-oxidative stability (Table 8).

CONCLUSIONS

I. During engine operation, lubricating oil accumulates not only insoluble eontaminanm, but also soluble
products of aging such as "resins" and also heavier substances that cannot be desorbed from silica gel by alcohol--
benzene or acetone--benzene mixtures. The relative content of hydrocarbon groups is thereby reduced, mainly
through "dilution ~ of the oil by aging products. The ratio of components in the total paraffinic-naphthenic and
aromatic fractions of the oil is changed only slightly by operation in the engine.
2. According to the infrared spectra, the paraffinlc-naphthenic fractions of new and used oils do not differ
substantially from each other.
3. The aromatic fractions of the used oil, in contrast to the fractions of the new oil, contain oxygen groups
that can be removed only by catalytic hydrotreating.

4. Oxygen groups in the aromatic fractions are den/mental to the thermal-oxidative stability of the oil.

LITERATURE CITED

I. E.G. Semenido, Conference on Viscosity of Liquids and Colloidal Solutions [in Russian], Izd. Akad. Nauk
SSSR, Moscow (1944), Part 2, pp. 21q-221.
2. B.V. Losikov, N. G. Puchkov, and B. A. Englin, Principles of Application of Petroleum Products [in Russian],
Gostoptekhizdat, Moscow (1959), p.. 401.
3. L.I. Bellamy, The Infrared Spectra of Complex Molecules, Methuen, London, 1954.
4. K . H . Rentrop, G. Kell, and H. Echardt, Schmierstoffe Schmierungstech., p. 16 (1967).

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