DEHYDRATION OF A DEPARAFFINATION SOLVENT BY EXTRACTION DRYING

N. M. Shakhova UDC 66.062:665.637.73

Deparaffination of raffinates with selective solvents in obtaining oils is a complex

and expensive process. Its technical-economic efficiency decreases significantly when the
solvent is flooded. Water enters the system of installations from difficult to eliminate
sources: with water vapor, the raw material, through leaks in the heat-exchange apparatus,
and is absorbed by the solvent from the inert gas. Moisture is liberated in the form of
a disperse aqueous phase with a decrease in the temperature of the solutions, and this compli-
cates maintenance of the technological conditions, increases energy expenditures, and de-
creases the yield of deparaffinated oil. Most of the circulating water is concentrated in
the gatch or petrolatum residue after low-temperature filtration of the raffinate and enters
the solvent regeneration unit [i].
Units for sedimentation and removal of the aqueous phase from the gatch solution tank
before the evaporation columns and the wet solvent container after the column are included
in the technological design of the installations. The analysis of the composition of the
equilibrium phases in the gatch solution tank showed that the solubility of water in the
petroleum product is 0.4-2 wt. % for a concentration of methyl ethyl ketone (MEK) in the
solvent (mixture of MEK with toluene) of 40-60%, respectively. The concentration of moisture
in the regenerated solvent varies from 0.6 to 2.6 wt. %.
The wet solvent sedimentation unit on the deparaffination installations of the Grozny,
Kremenchug, and Novo-Yaroslavl refineries practically did not work, since the temperature
of the solvent after the air condensers-coolers is usually 50-60~ and all of the entering
moisture is in the dissolved state. Separation of the MEK-toluene-water mixture from the
strippers, which contained a large amount of toluene (40-50 wt. %) and water (30-40 wt. %)
in the settling tank produces a solvent with 0.2-0.4 wt. % water.
The analysis of the operation of the water circuit demonstrated the possibility of
drying the wet gatch solution by extraction. Dehydration of the "wet" solvent implies bring-
ing the deparaffinated oil containing up to 0.3 wt. % water removed from the solution to
the "dry" level. The phase equilibrium of these systems was studied at temperatures of 20-
600C to obtain more complete data on the process of sedimentation of the three-component
MEK-toluene-water and four-component petroleum product-MEK-toluene-water systems. The ques-
tions of the solubility of water in the MEK-toluene solvent are treated in [2, 3]. The tri-
angular composition-property diagrams were used to describe the phase equilibrium in these
systems. Solvents of a high degree of purity were used in the experiments. The composition
of the equilibrium phases was determined by gas-liquid chromatography; the experimental data
were described mathematically.

TABLE i
Used' wt. % I Obtained, ~. %
I solvent aqueous phase
MEK toluene water MEK Itoluen~ Water MEK Itoluenelwater
45 45 0 Homogeneous solution
0 45 45 0 99,93 0,07 0 0,06 99,94
45 0 45 88.00 0 12.00 18,60 0 81,40
5 50 45 9,40 90,46 O. 14 0,54 0,06 99,40
lO 45 45 15,55 84,24 0,21 0,84 0,06 99. I0
20 41 39 30,02 65.50 0.48 2,17 0.07 97,76
35 45 20 43,00 56,01 0,99 . 5,00 0,07 94,93
40 37 23 50,00 48,59 1,41 7.12 0,07 92,8 l
50 31 19 59.30 38,30 2,40 9,01 0,07 90,92
64 26 10 68,50 27,59 3,91 12,20 0,08 87,72
80 1l 9 80,9 i l l, 1 l 7.98 I b,24 0,08 83.68

Grozneftekhim Scientific and Industrial Association. Translated from Khimiya i Tekh-

nologiya Topliv i Masel, No. 2, pp. 30-31, February, 1990.

104 0009-3092/90/0102-0104512.50 9 1990 Plenum Publishing Corporation

 MEK

Fig. i. Solubility isotherm of the MEK-tolu-

ene-water system at a temperature of 40~

f o o ~ ~ o
o 2g t+g 6g 80 100%
To luene Water

TABLE 2
Temperature [ Coefficient
of equilib- [
rium system~ A
~ !

For equation (i)

60 0,1233 0,0537 0,9992
40 0,0922 0,0551 0,9995
20 0,0611 0,0577 0,9994
For equation (2)
60 --1,8610 0,9270 0,9999
40 --1,8160 0.9080 0,9999
20 --1,7420 0,8730 0,9999

TABLE 3
Used Obtained
Indexes water solvent I aqueous phase
g a t c h I MEK etOelU
- gatch I MEK ]to lunelwater gatch I MEK !tolueneIwater

Setling of gatch solution

Amount of phases, g 100,00 97,72 2,28
Composition, wt. %
solution 20,00 4 8 , 0 0 28.80 3,20 2 0 . 4 6 3 8 , 9 7 39.39 1,18 Traces 9,36 0,07 90,57
solvent -- 60,00 36,00 4,00 -- 49,00 49,53 1,47 -- 9,36 0,07 90,57
Settling of gatch solution together with flooded solvent (15 wt. %)
Amount of phases, g 112,72 105,03 7,69
Composition, wt. %
solution 17,74 3 6 , 2 7 38,76 7,23 19,04 31,I7 49,1 I 0,68 Traces 7,83 0,07 92,10
solvent -- 44,09 47,13 8,78 -- 38,50 60,67 0,83 -- 7,83 0,07 92.10
Settling of gatch solution together with flooded solvent (15 wt. %) and gatch (38 wt. %)
Amount of phases, g 145,03 144,21 0,82
Composition, wt. %
solution 47,31 2 2 , 5 7 35,57 0,49 41,61 13,20 45,01 0,[8 Traces 4,17 0,07 95,76
solvent -- 38,50 60,68 0,84 -- 22,60 77,08 0,32 -- 4,17 0,07 95,76

The compositions of the equilibrium phases of the MEK-toluene-water system at the tem-
perature of 40~ are reported in Table 1 and the corresponding solubility isotherm is shown
in Fig. i. This system concerns type 2 (Treybal classification [4]) and contains two pairs
of partially miscible liquids. The left branches of the binodal curves in the temperature
range studied are best described by the equation

z , = Aexp(Bxl) (1)

where zz and x z are the concentration of water a n d MEK i n the solvent, wt. %, r e s p e c t i v e l y .
The values of coefficients A and B in Eq. (!) for temperatures of 20-60~ obtained
by processing the data with the method of least squares, are reported in Table 2. Selected
correlation coefficients R are also reported there. Their closeness to one indicates the
satisfactory correlation of the experimental and calculated values of z I. The position of
the tielines (lines connecting the compositions of the equilibrium phases) in the ternary
diagrams is described by the linear logarithmic dependence

105
 iog(g,/z2) = A + Blgz~ (2)
where Yl is the concentration of toluene in the solvent, wt. %; z 2 is the concentration of
water in the aqueous phase, wt. %.
The values of coefficients A and B in Eq. (2) and correlation coefficient R for tempera-
tures of 20-60~ are reported in Table 2. The concentration of water z 2 in the equilibrium
aqueous phase as a function of the concentration of toluene Yl in the solvent was determined
with the equation

z~=y,/le+8~g~' (3)
The analysis of the isotherms and data from the laboratory studies showed that changing
the composition of the starting mixtures to an increase in the concentration of toluene and
water results in a decrease in the concentration of moisture in the equilibrium phase of
the solvent. Settling of moist gatch solution (350-420~ fraction) with 20 wt. % petroleum
product and 60 wt. % MEK thus results in a solvent containing 1.47% water (Table 3). Settling
of this gatch solution together with a flooded solvent (15 wt. % for the gatch solution)
permits decreasing the concentration of water to 0.83% in the solvent and 0.68 wt. % in the
gatch solution. In the case of processing high-boiling raw material and using a solvent
with a lower concentration of MEK (40 wt. %), addition of a flooded solvent results in a
decrease in the moisture content to 0.3 wt. %.
In the example examined, more complete elimination of water is ensured by recirculation
of the gatch flow delivered in the amount of 38 wt. % to the starting mixture with a subse-
quent stage of evaporation of the solvent. As Table 3 shows, extraction of MEK from a wet
gatch solution by currents of toluene and petroleum product decreases the solubility of water
in the gatch solution to 0.18 wt~ % and to 0.32 wt. % in the regenerated solvent. Similar
calculations show that in processing of raffinates which boil out within the limits of 420-
490~ in the presence of a solvent containing 50 wt. % MEK, the required amount of recircu-
fating gatch is significantly less and consists of 15 wt. % for products subject to settling.
It is thus recommended that the gatch solution be settled together with the flooded
solvent by feeding the circulating gatch into the settling zone if necessary to bring the
concentration of moisture in the solvent to the "dry" level.

LITERATURE CITED
I. N. M. Shakhova, V. M. Evtushenko, A. P. Grishin, et al., Neftepererab. Neftekhim., No.
3, 8-11 (1986).
. Yu. N. Roshchin, G. P. Vazhnova, and L. P. Shkarupa, ibid., No. 9, 11-12 (1981).
3. A. N. Leonidov, V. V. Ivanova, L. P. Shkarupa et al., ibid., No. 3, 15-17 (1983).
4. R. E. Treybal, Liquid Extraction, 2nd edn., McGraw-Hill, New York (1963).

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