Indi an Journal of Chemi cal Technology

Vol. 6, March 1999, pp. 85 -89

Extraction of aromatics from naphtha reformate using combination solvents

Mao nra njan Saha a *, B S Rawat b , M K Khanna b , B R Nautiya l ~ & M V Raghuram b
., Dcpanment of Applied Chemistry and Chemical Technology, Universi ty of Dhaka, Dhaka 1000, Bangladesh
b Indi an Insti tute of Petroleum, Del, ,.adun 248 005 , India

Received 7 Febm ar), 1997: accepted 13 Jal/I/nt)l l999

Two combi nati on solvents, VI Z. tetrac lh yleneglycol-N-meth ylpy rrol idone an.d tetraeth yleneglycol-N-
for mylmorpholine were used for the ex tract ion of aro matics fro m naphtha refo rmate conta ini ng 46 .5% aro mat ics and the
phase equilibria we re determined at 40C. The data were correlated using Bachman, Othmer-Tobi as and Hand Coord inates.
'1

Ex traction of aromatic hydrocarbon s from multicom-
ponent hydroca rbon mixtures is of great commercial
importan ce in the petro leum refining indu stry . There
exists a number of co mmerci a l extraction processes
for the extracti o n of aromatic s from aliphatics using
the hi ghl y po lar, hi g h den sity and high boiling point
so lvents such as dimethy ls ulfoxide I , N-
methylpynolidone (NMP) 2, N-formylmorpholine
(N FM)'14, g lyco ls5-7 and s ulfolane 8 . ' I Solvents for ex-
traction should have high se lectivity for aromatics ,
)
hi gh capacit y, capability to form two phases at ex -
trac tion temperature s, capab ility of rapid phase sepa-
ration , good thermal stability and should be non-
conosive and non-reac ti ve 7. 12. 14. Work is still in prog-
ress for exploring other solvents with these proper-
ti es 15 19 . The other approach is to use a combination
of solvents so as to balance the selectivity and sol-
vency function s 20.27 Such a combination of solvents
is reported to g ive the advantage s of lower consump-
tion of energy, lower solvent to feed ratio, with a con-
seque nt in the dimension of the column 15.
The aIm of the presen t investigation is to study the
liquid-liquid eq uilibria for th e extraction of aromatic s
from naphtha reformate using two new combination
so lvents. namely , tetraethyleneglycol (tetra)-NMP
and tetra-NFM .
Experimental Procedure
The propertie s of th e fe ed (naphtha reforma te) and
th e solvents used in the exper iments are li sted in Ta-
bl es I and 2 re spectI ve ly.
Equililmum mea surement s on the sys te ms were
*Forcorrespo nden cc.
made in g lass jacketed mixer-sett ler 28 controlled at a
temperature of 40C by circulation of water through
the external jacket from a thermostatic bath. Specific
amounts of the feed and the combination solvent were
taken into the cell and stined for 10 min , whi ch is
suffici ent len gth of time as determined in trial ex-
periments for establi shment of eq uilibrium betwee n
phases. The equilibrium phases were then a llowed ~o
settle for 10 min , and were separately withdrawn and
analysed. Solvent was re mo ved from the raffinate
phase by water-wa shin g and from the extract ph ase
by azeotropic di stillation w ith wa ter. The arom atic
contents in the extract and raffinate were determ ined
by gas-liquid chromatography . The analytical tech-
nique has been standardi sed and reported e lsewhere '6 .
Results and Discussion
The meas ured liquid-liquid equilibrium compo si -
tions of the equilibrium phases of naphtha reformate
at 40C with combination solvent systems tetra-NMP
(70:30 by wt) and tetra-NFM (70 :30 by wt) are given
in Tables 3 and 4, respectively. To cover the entire
region of phase diagram , the solvent to feed mass
ratio wa s va n ed from 0.5 to 3.0. The tie line data for
the systems are observed to fit well in the smooth
binodal curves as shown in Figs I and 2, indi cat in g
the accuracy of the experimental tie line data . The
solubility curves (Fig. 3) show that the so lubility of
hydroca rbon s in the extract phase de'c reases with the
increase in the solvent to feed ma ss ratio . But the ab-
so lute quantity of the hydrocarbon s in the ex tract
phase increases when the solvent to feed ratio is in-
creased. The effectiveness of extraction of aromatic s
by a so lvent depends on its selectivity and capacity,
86 INDIAN J CHEM . TECHNOL., MARCH 1999

which for the present systems can be observed in Figs
4 and 5. The tetra-NFM system has higher selectivity
and lower capacity compared to those of the tetra-
NMP system. Moreover, viscosities of the concerned
combination solvent systems are very low compared
to the viscosity of the pure tetra (Table 2 ) which will
result in providing higher efficiency for aromatics
extraction.
The experimental data were correlated using
Bachman 29 , Othmer-Tobias 30 and Hand 3 1 coordinates

Table I-Characteristics of the feed (naphtha reforrnate 60-90C) AROMATICS

I

Characteristics

/;
ASTM distillation
Initial boiling point, at C 52.6
5% vol, at C 68. 1
10% vol, at C 69.5
20% vo l, at C 69.5
30% vol , at C 70.7
40% vol, at C 71.4
50% vol, at C 72.2
60% vo l, at C 73 .1
70% vo l, at C 74.2
SO% vol, at C 75 .6
90% vol, at C 77.7
95% vol, at C 79.2
Final boiling point, at C 94.9
Recovery, % by vo l 98 .3
Residue, % by vol 0.8 ~~~-i~~~~,--~~~~~~~~~~~~~~~~,~
Loss, % by vol 0.9 ----NONARCtdATlCS. ""T. %
NONAROMATICS ... SOLVENT
Density at 20C, g/cm 3 0.7659
Refractive index, no20 1.4300 Fig. I-Liquid-Iiquid equi librium for thl system reforrnate (60-
Aromatics (wt %) 46.5 90C) - tetra + NMP ~t 40C

Table 2-Properties of the solvents

Solvent n0 20 d4 20 B.P.,oC M.P.,oC Flash Viscosity, cSt Other properties

point
Tetraethyleneglycol 1.4609 1.1285 328 -6.2 345 OF at 20C, 55, Soluble in water
(Tetra) 40 C, 55 benzene, toluene;
hygroscopic liquid

N-fo rmylmopholine 1.4 8696 1. 1528 244 20 124 C at 20C, 8.13 Specific heat, cal/g/
(NFM) 40C, 3.5 C at
50 C, 3.61 25C, 0.38
70C,2.45 80C, 0.43
Heat of vapo urisa-
tion,
cal/g mole at
1'27 C, 12000
244 C, I I 000

N-Methyl pyrrolidone 1.4703 1.033 204 -24 95-97C at 20 C, I. 79 Miscible in water and
(NM P) 40 C, 1.60 organic solvents.
Specific heat, 0.40
kcallkg at 206C

Tetra -NFM at 40 C, 13.69

(70:30 by wt)
Tetra-NM P at 40 C, 9.0 1
(70:30 by wt)
 SAHA et a/.: EXTRACTION OF AROMATICS 187

ARO\1ATICS WT. 'II. AROMATICS IN RAFFINATE PHASE

Ov _____2~0~--~40~--~60~----~8~0----j;
100'-

80
SELECT7V1TY
CU
......,.
___ - _
--'"'"', ....... ,
..... ....
....

/
i f eo
~
f'~
40
-t-
~
~

~ 60
2
I
A.:
~. . ~

'*' ..... 00 I:i

~
'-""
, eo \

, 70
III
U
~
"l
40

~
\
i"l 20
~
; O~~ __L __ _ _ _ ~_ _ _ _~_ _ _ _~----~

- 100 o 20 40 100
.0 TO eo 10 4O .0 00
NON AROMATICS WT'II. AROMATICS IN RAFFINATE
NON AROMATICS,WT.% SOLVENT

Fig. 4--Selectivity and distribution curves for the naphtha refor-

Fig. 2-Liquid-liquid equilibrium for the system reformate (60-
mate to combination solvent at 40C. Combination solvents: 1-
90C) - tetra + NFM at 40C
tetra-NMP; 2- tetra-NFM

30r-----------------------------------, --.. 0 6

211 ;1
it", 0.5
0
2

~ti 0
20
u z
~ -
...
II: ...
~
I:i ~ 0 4
z 3
~ III ;;;1/)
t:: u~
-'
II
~ 2
i=
~
ti:i 0 .3
-'
~IO ~o
II: II:
<I ~

~~
~Ii
0 .2
II

---- ..:
0.1 I I
0~-------~-------12----------~3~--~ 0
<I
35 40 45
20 25 30
MASS RATIO OF SOLVENT TO FEEO ( S/F I
WT. 'Yo AROMATICS IN RAFFINATE PHASE

Fig. }-Solubility curves with varying mass ratio of naphtha

reformate to combination solvent at 40C. Combination solvents: Fig. 5--Comparison of capacity of combination solvents with
1- tetra-NMP; 2- tetra-NFM naphtha reformate at 40C : 1- tetra-NMP; 2- tetra-NFM

Table 3--Experimentalliquid-liquid equilibrium compositions for non-aromatics-aromatics-tetra-NMP at 40C

WI. percentage in raffinate phase WI. percentage in extract phase

Non-aromatics Aromatics Tetra-NMP Non-aromatics Aromatics Tetra-NMP

52.5 39.1 8.4 2.6 22.2 75 .2

58 .7 34.0 7.3 3.2 17.6 79.2
67.3 26.4 6.3 3.6 13.5 82.9
72.4 22 .5 5. 1 3.6 10.8 85 .6
88 INDIAN J CHEM. TECHNOL., MARCH 1999

Table 4-Experimentalliquid-liquid equilibrium composi tions for non~aromatics-aromatics-tetra-NFM at 40C

Wt. percentage in raffin ate phase WI. percentage in extract phase

No n-aro matics Aromatics Tetra-NFM Non-aromatics Aromatics Tetra-NFM

53.4 40.6 6.0 1.7 22.1 76.2

57 .7 36.4 5.9 2.0 16.1 81.9
65 .7 29.3 5.0 2.0 12.2 85.8
70 .0 25.0 5.0 2.2 9.9 87.9

o~----------------------------~
80~----------------------------~
~

)(
..
.....
III

/:
U
)(

.. -0.'
~

.0

- I L -________ ~ ________ ~ ________ ~

711 -I -0. & 0 0.&

Log t XCA!XAA )

70L---________ ~L- ____________ ~

Fig. 8--Hand corre lation for naphtha reformate-combination
'1 1.50 so lvent system s at 40C. Combination solvents: 1- tetra-NMP; 2-
tetra-NFM .

Fig. 6--Bac hman correlation for naphtha reformate-combination and the plots are shown in Figs 6-8. Since the data do
sol vent systems at 40C : 1- tetra-NMP ; 2- tetra-NFM not exhibit much scatter from straight line, they are
judged acceptable on the empirical basis, indicating
internal consistency of the experimental data.

-0 .4 ~-------------------------, Acknowledgement
One of the authors (Manoranjan Saha) is grateful
to the Third World Academy of Sciences (TWAS),
Trieste, Italy and the Council of Scientific & Indus-
trial Research (CSIR), New Delhi, India for awarding
a Post Doctoral Research Fellowship.

Nomenclature
X = liquid phase concentration , wt fraction.

Subscripts
A = non-aromatics
B = so lve nt
C = aromatics
AA , CA = concentrat io n (wt. fraction) of components A and C
res pectively, in phase A (non-aromatics-rich phase)
BB, CB = concentration (wI. frac ti on) of components Band C,
res pectively in phase B(solvenl-rich phase).

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 SAHA et al.: EXTRACTION OF AROMATICS 89

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