Chemistry and Technology of Fuels and Oils, Vol. 42, No.

6, 2006

USE OF USED CLAY FROM OIL PRODUCTION

G. D. Lyakhevich, V. A. Grechukhin, and A. G. Lyakhevich UDC 665.54:543

The results of a physicochemical study of the organic mass of used clay from production of mineral oils
are presented. The clay is hydrophobized, almost does not swell in water, and for this reason can be
recommended for use in production of waterproofing materials.

Used bleaching clay is a production waste in after-cleaning of lube oil cuts. However, it has not been
used in practice, which results in environmental pollution [1] and loss of valuable mineral raw materials for the
construction industry and other industrial sectors.
We investigated the basic properties of used clay (UC). In the future, this will make it possible to find
ways of rationally and environmentally safely utilizing it.
UC from the oil contact treatment unit at Naftan Industrial Association (UC-1) and from burial sites in the
Polotsk region (UC-2) were used for the studies. The studies were conducted with the methods described
in [2-10]. The results are reported in Table 1.
For a more exhaustive study, the samples of UC were separated and the physicochemical properties of the
components obtained were determined.
The organic mass was separated with the following method. Approximately 500 g UC was loaded in a
heated column and heated to 45±5°C. Benzene was added at the top of the column through a reflux condenser and
desorbate (organic mass and solvent) was taken off into a tank at the bottom of the column.
After distillation of the benzene and blowing with nitrogen, the organic mass was used for
the studies. The desorbent (benzene) flow rate was 5 vol. pts. per 1 vol. pt. UC. After separation of the
organic part, the residue was heated to 105±5°C and blowing through at the same temperature with an inert
gas – nitrogen – for 60 min to more completely eliminate the benzene.
The physicochemical properties of samples of organic mass OM-1 and OM-2 separated from samples of
used clay UC-1 and UC-2 are reported in Table 2

____________________________________________________________________________________________________
Belorussian National Technical University. Translated from Khimiya i Tekhnologiya Topliv i Masel,
No. 6, pp. 33 – 35, Novemmber – December, 2006.

0009-3092/06/4206–0431 © 2006 Springer Science+Business Media, Inc. 431

Table 1

Used clay
Indexes
UC-1 UC-2
Color Light yellow Dark brown
3
Real density, kg/m 1894.2 1845.6
Dielectric constant 24.5 18.1
Swelling in water at 20°C Does not swell
Moisture content, wt. % 1.43 0.96
Ash content, wt. % 61.85 59.12
Content, wt. %
sulfur (total) 0.34 0.37
volatiles 42.45 43.7

Table 2

Organic mass
Indexes
OM–1 OM–2
Density at 20°C, kg/m3 937.4 941.3
Refractive index 1.5705 1.5794
Molecular weight 424 418
Viscosity at 100°C, mm /sec 2
6.5 5.2
Flash point (open cup), °C 229 231
Low heat value, J/g 41 163 40 643
Sulfur content, wt. % 1.18 1.27
Ash content, mg KOH/g 0.007 0.009
Acid number, mg KOH/g 1.25 1.27
Elemental composition, wt. %
carbon 86.36 86.23
hydrogen 10.98 10.92
sulfur 0.69 0.76
nitrogen 1.14 1.18
oxygen 0.83 0.91
H:C atomic ratio 1.526 1.52
Empirical formula C30.49H46.19S0.09N0.08O0.24 C30.01H45.28S0.10N0.35O0.24

The group chemical composition of the organic mass of UC was determined in a column
with KSK large-pore silica gel (0.25-0.5 mm fraction) [5]. The silica gel was first washed with hot distilled water
and dried for 6 h at 105°C and 6 h at 160°C. Mixtures of petroleum ether and benzene in different proportions were
used for desorption of hydrocarbons and resins. The solvents were distilled off the hydrocarbon fraction and
resins in a water bath.
The data obtained (Table 3) indicate an important content of paraffins and naphthenes in the organic
mass.

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 100

Absorbtion, %
50

0
700 900 1100 1300 1500 2800 3000
-1
Wave number, cm

Fig. 1. IR spectra of organic mass separated from used clay: 1) OM-1; 2) OM-2.

Table 3

Content (wt. %) in organic mass

Compounds
OM–1 OM–2
Hydrocarbons 94.1 94.6
paraffins and naphthenes 23.8 20.6
aromatics
monocyclic 22.1 23.7
bicyclic 24.5 26.2
polycyclic 23.7 24.1
Resins 5.9 5.4

The structure of the hydrocarbons in the organic mass was investigated by IR spectroscopy [8-11]. The
spectra (see Fig. 1) were made on a UR-20 universal spectrophotometer in the 700-3600 cm-1 frequency range. Their
analysis showed characteristic fluctuation of the intensity of the absorption bands of methyl and methylene
groups in the 2960, 2930, 1465, and 1380 cm -1 regions. The absence of the 720 cm-1 band indicated the insignificant
content of aliphatic structures in the organic mass and that they are represented by short alkyl chains with less
than four carbon atoms.
The oxygen-containing functional groups in the organic mass were determined by the method in [3]:
carboxyl groups by potentiometric titration of the organic mass dissolved in alcohol–benzene
mixture (1:3) to pH 10 with 0.05 N KOH solution;
ester groups by addition of 0.1 N alcohol solution of KOH to the organic mass; the mixture was boiled
for 18 h, then 20 ml of 0.1 N titrated alcohol solution of HCI was poured in and it was titrated while stirring
constantly in 0.1 N alcohol solution of KOH to pH 10 [5];

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Table 4

Content (mg KOH/g) in organic mass

Functional groups
OM–1 OM–2
Carboxyl –COOH 1.25 1.27
Ester –RCOOH 2.14 2.31
Carbonyl =C=O 3.86 3.78
Hydroxyl –OH 5.07 6.12

carbonyl groups by mixing the organic mass with 10 ml of ethanol and 2 ml of water–alcohol solutions of
hydroxylamine hydrochloride; the mixture was boiled for 18 h, cooled to room temperature, 20 ml of water was
added, and it was then titrated potentiometrically with 0.1 N aqueous solution of KOH to pH 3.5;
hydroxyl groups using pyridine; a solution of the organic mass was titrated with 0.1 N aqueous solution
of KOH to pH 10.
Two samples of organic mass were used to determine the carboxyl, ester, and carbonyl groups and three
were used to determine the hydroxyl groups. The results of the determinations are reported in Table 4. The high
hydroxyl group content in both OM-1 and OM-2 is probably due to the conditions of storage and shipment
of the UC exposed to atmospheric oxygen and the catalytic effect of the clay.
The important content of oxygen-containing functional groups in the organic mass indicates the expediency
of using it as an additive to waterproofing materials to increase their adhesion to concrete surfaces.
These studies provided a deeper understanding of the properties of UC and predicting its qualified use
for production of waterproofing materials with improved adhesive and plastic properties.

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