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SEPARATION OF m-XYLENE FROM o-XYLENE BY

EXTRACTIVE DISTILLATION
a a
LLOYD BERG & AN-I YEH
a
Montana State University , Bozeman, MT, 59717
Published online: 03 Apr 2007.

To cite this article: LLOYD BERG & AN-I YEH (1987) SEPARATION OF m-XYLENE FROM o-XYLENE BY EXTRACTIVE DISTILLATION,
Chemical Engineering Communications, 54:1-6, 149-159, DOI: 10.1080/00986448708911904

To link to this article: http://dx.doi.org/10.1080/00986448708911904

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 Chem. Eng. Cornrn. 1987, vol54, pp. 149-159
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Printed in the United States of America

SEPARATION OF m-XYLENE FROM

0-XYLENE BY EXTRACTIVE DISTILLATION
LLOYD BERG and AN-I YEH
Montana State University, Bozeman, MT. 5971 7
Downloaded by [University of Sussex Library] at 07:10 14 January 2015

(Received August 18, 1986; in final form January 12, 1987)

m-Xylene is difficult to separate from 0-xylene by rectification because the relative volatility is only
1.12. rn-Xylene can be separated from 0-xylene using extractive distillation in which the extractive
agent is composed o f the proper higher boiling organic compounds. Typical effective agents are
benzoates, DMSO, DMFA, adiponitrile, rnaleic anhydride, phthalic anhydride, polychloroaromatics
and sulfolane.
KEYWORDS Separation m-Xylene 0-Xylene Extractive distillation

INTRODUCTION

Extractive distillation is the mehtod of separating close boiling compounds by

carrying out the distillation in a multiplate rectification column in the presence of
an added liquid or liquid mixture, said liquid(s) having a boiling point higher that
the compounds being separated.
The xylenes are major precursors to many processes for making plastics and
dyes. In these uses it is absolutely essential that the xylenes be very pure. It is the
presence of impurities that makes them poor polymerizing agents as a plastic or
render them inconsistent as dye intermediates. The xylenes of commerce
originate either from coal tar or from petroleum, usually via the hydroforming of
the corresponding naphthenes and thus are always found as mixtures of isomers.
Frequently the p-xylene is removed by freezing leaving a mixture of m-xylene and
o-xylene, the basis of this investigation. Thus the separation of pure m-xylene
from o-xylene remains to be accomplished by some other method. The difficulty
of this separation can be shown by referring to Table I, values for which were
derived from the Fenske equation. The relative volatility of m-xylene to o-xylene
is 1.12. To separate these two by conventional rectification in 95% purity requires
a minimum of 52 theoretical plates at total reflux. With actual plates of 75%
efficiency, it requires 70 plates. Extractive distillation would be an attractive
method of separating m-xylene from o-xylene if effective agents can be found
which will markedly increase the relative volatility. Berg (1983) reported the
separation of benzene and toluene from close boiling non-aromatic hydrocarbons
by extractive distillation. Berg (1982, 1983) also reported the separation of
ethylbenzene from xylenes.
 L. BERG AND AN-I YEH
TABLE I

Theoretical and actual plates required vs. relative volatility for m-xylene-o-xylene saparation

Relative Theoretical plates required Actual plates

volatility at total reflux, 95% purity required, 75% Eff.
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RESULTS AND DISCUSSION

The objective of this investigation was to find compounds and/or mixtures which
would be capable of enhancing the relative volatility of m-xylene to o-xylene. A
large number of possible extractive agents were evaluated in a glass Othmer type
vapor-liquid equilibrium still. The mixture tested was 50% m-xylene-50%
o-xylene. Six to twelve hours of operation were allowed to attain equilibrium and
the amount of extractive agent was in the range of one to two parts per part of
xylene mixture. Analyses were by means of gas chromatography. The solvent
mixtures were equiproportional. The successful agents are presented in Tables
11-IX. Table I1 lists dimethylsulfoxide (DMSO) and its mixtures which are

TABLE I1

Relative volatilities of mixtures containing dimethylsulfoxide (DMSO)

Relative
Extractive distillation agents volatility

DMSO 1.30
DMSO, Benzonitrile 1.30
DMSO, Phthalic anhydride 1.32
DMSO, 1,4-Butanediol 1.35
DMSO, Butyl p-hydroxy benzoate 1.39
DMSO, Diethylene glycol 1.35
DMSO, Hydroquinone 1.32
DMSO, Catechol 1.35
DMSO, Tetraethylene glycol 1.35
DMSO, Sulfolane 1.31
DMSO, bis-Phenol A 1.35
DMSO, Dihexyl phthalate 1.33
DMSO, Diphenyl isophthalate 1.39
DMSO, Dioctyl phthalate 1.36
DMSO, Dibutyl phthalate 1.32
DMSO, n-Octanol 1.32
DMSO, Ethylene glycol phenyl ether 1.34
DMSO, Benzyl alcohol 1.33
DMSO. Diisodecyl phthalate 1.33
 SEPN. OF m-XYLENE FROM a-XYLENE BY EXTR. DISTN. 151
TABLE II (Continued)

Relative
Extractive distillation agents volatility

DMSO, Ethyl benzoate 1.34

DMSO, Dodecenyl succinic anhydride 1.31
DMSO, Butyl benzoate 1.33
DMSO, Diisooctyl phthalate 1.33
DMSO, Nitrobenzene 1.35
DMSO, Ethylene carbonate 1.34
DMSO, Ethylene carbonate, Adiponitrile 1.31
DMSO, Ethylene carbonate, Diethylene glycol 1.32
DMSO, Ethylene carbonate, 1,4-Butanediol 1.33
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DMSO, Propylene carbonate, Adiponitrile 1.32

DMSO, Propylene carbonate, Diethylene glycol 1.33
DMSO, Benzyl benzoate 1.34
DMSO, Methyl salicylate 1.39
DMSO, Adiponitrile, Glycerine 1.31
DMSO, Adiponitrile , Diphenyl isophthalate 1.39
DMSO, Adiponitrile, Acetophenone 1.33
DMSO, Adiponitrile, Ethylene glycol phenyl ether 1.33
DMSO, Adiponitrile, Nitrobenzene 1.30
DMSO, Adiponitrile , Dibutyl phthalate 1.31
DMSO, Adiponitrile, Ethyl benzoate 1.30
DMSO, Adiponitrile, Diethylene glycol 1.35
DMSO, Ethylene glycol, Ethyl acetoacetate 1.37
DMSO, 1,5-Pentanediol, Nitrobenzene 1.35
DMSO, Dipropylene glycol, Nitrobenzene 1.31
DMSO, Diethylene glycol, Nitrobenzene 1.36
DMSO, Sulfolane,IA-Butanediol 1.35
DMSO, Dimethylformamide, 1,4-Butanediol 1.30
DMSO, Ethyl benzoate, Diiscoctyl phthalate 1.34
DMSO, Ethyl benzoate, Ethylene glycol phenyl ether 1.30
DMSO, Ethyl benzoate, Dioctyl phthalate 1.34
DMSO, Nitrobenzene,IA-Butanediol 1.30
DMSO, Nitrobenzene, Ethylene glycol phenyl ether 1.32
DMSO, Ethyl benzoate, Benzyl butyl phthalate 1.31
DMSO, Ethyl benzoate, Diphenyl isophthalate 1.35
DMSO, Ethyl benzoate, Ethylene glycol phenyl ether 1.31
DMSO, Dodecenyl succinic anhydride, Ethylene glycol phenyl ether 1.31
DMSO, Adiponitrile, Propyl p-hydroxy benzoate 1.37
DMSO, Adiponitrile, Butyl p-hydroxy benzoate 1.38
DMSO, Adiponitrile, Methyl salicylate 1.35
DMSO, Adiponitrile, bis Phenol A, Butyl p-hydroxy benzoate 1.31
DMSO, Butyl benzoate, Propyl p-hydroxy benzoate 1.35
DMSO, Butyl benzoate, Ethyl p-hydroxy benzoate 1.35
DMSO, Butyl benzoate, Methyl p-hydroxy benzoate 1.31
DMSO, Methyl benzoate, Diphenyl isophthalate 1.38
DMSO, Benzyl butyl phthalate, Diphenyl isophthalate 1.39
DMSO, Diphenyl isophthalate, Ethyl salicylate 1.32
DMSO, Diphenyl isophthalate, Butyl benzoate 1.35
DMSO, Diphenyl isophthalate 1.34
DMSO, Diethylene glycol, Methyl benzoate 1.34
DMSO, Diethylene glycol, Ethyl benzoate 1.36
DMSO, Diethylene glycol, Butyl benzoate 1.36
DMSO, Diethylene glycol, Benzyl benzoate 1.36
DMSO, Diethylene glycol, Methyl salicylate 1.35
DMSO, Diethylene glycol, Ethyl salicylate 1.39
 152 L. BERG AND AN-I YEH
TABLE III

Relative volatilities of m-xylene-o-xylene with mixtures containing benzoates

Relative
Extractive distillation agent volatility

Methyl benzoate, Butyl benzoate 1.33

Methyl benzoate, Ethyl benzoate 1.34
Methyl benzoate, Diisodecyl phthalate 1.30
Methyl benzoate, Diphenyl isophthalate 1.35
Methyl benzoate, DMSO, Butyl benzoate 1.38
Methyl benzoate, DMSO, Ethyl benzoate 1.33
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Ethyl benzoate, Diphenylterephthalate 1.31

Ethyl benzoate, Ethylene glycol phenyl ether 1.33
Ethyl benzoate, Dimethyl phthalate 1.30
Ethyl benzoate, DMSO, Butyl benzoate 1.31
Ethyl benzoate, Ethylene glycol phenyl ether, Methyl salicylate 1.31
Ethyl benzoate, Ethylene glycol phenyl ether, Benzyl alcohol 1.30
Ethyl benzoate, Butyl benzoate, Benzyl butyl phthalate 1.31
Butyl benzoate 1.33
Butyl benzoate, Diphenyl iosphthalate 1.35
Benzyl benzoate, Benzyl butyl phthalate 1.32
Benzyl benzoate, Ethyl-4-hydroxybenzoate 1.33
Benzyl benzoate, Methyl-4-hydroxybenzoate 1.31
Benzyl benzoate, Ethyl-2-hydroxybenzoate 1.39
Benzyl benzoate, Methyl-2-hydroxybenzoate 1.38
Benzyl benzoate, Butyl benzoate 1.31
Benzyl benzoate. Benzoic acid 1.32
Benzyl benzoate, DMSO, Methyl-2-hydroxybenzoate 1.42
Benzyl benzoate, DMSO, Ethyl-2-hydroxybenzoate 1.33
Benzyl benzoate, DMSO, Methyl benzoate 1.34
Benzyl benzoate, DMSO, Ethyl benzoate 1.35
Benzyl benzoate, DMSO, Butyl benzoate 1.34
Benzyl benzoate, DMSO, Benzoic acid 1.32
Methyl-2-hydroxybenzoate 1.39
Methyl-2-hydroxybenzoate, Diisononyl phthalate 1.32
Methyl-2-hydroxybenzoate, Butyl benzoate 1.32
Methyl-2-hydroxybenzoate, Benzyl benzoate 1.37
Methyl-2-hydroxybenzoate, Methyl benzoate 1.30
Methyl-2-hydroxybenzoate, DMSO, Butyl benzoate 1.34
Methyl-2-hydroxybenzoate, DMSO, Ethyl benzoate 1.33
Methyl-2-hydroxybenzoate, DMSO, Methyl benzoate 1.37
Butyl-4-hydroxybenzoate, bis-Phenol A 1.34
Ethyl-2-hydroxybenzoate 1.34
Ethyl-2-hydroxybenzoate. Methyl benzoate 1.35
Ethyl-2-hydroxybenzoate, Butyl benzoate 1.33
Ethyl-2-hydroxybenzoate, Methyl-2-hydroxybenzoate 1.36
Ethyl-2-hydroxybenzoate, Ethyl benzoate 1.30
Ethyl-2-hydroxybenzoate, DMSO, Methyl benzoate 1.37
Ethyl-2-hydroxybenzoate. DMSO, Ethyl benzoate 1.32
Ethyl-2-hydroxybenzoate, DMSO, Butyl benzoate 1.35
Ethyl-2-hydroxybenzoate, DMSO, Methyl-2-hydroxybenzoate 1.31
Ethyl-2-hydroxybenzoate, Diphenyl iosphthalate 1.32
Diethylene glycol dibenzoate 1.30
Diethylene glycol dibenzoate, Methyl benzoate 1.34
Diethylene glycol dibenzoate, Ethyl benzoate 1.36
Diethylene glycol dibenzoate, Benzyl benzoate 1.35
Diethylene glycol dibenzoate, Butyl benzoate 1.30
Diethylene glycol dibenzoate, Methyl-2-hydroxybenzoate 1.31
 SEPN. OF m-XYLENE FROM a-XYLENE BY EXTR. DISTN. 153
TABLE III (Continued)

Relative
Extractive distillation agent volatility

Diethylene glycol dibenzoate, Ethyl-2-hydroxybenzoate 1.39

Dipropylene glycol dibenzoate (DPGDB) 1.33
DPGDB, Diphenyl isophthalate 1.34
DPGDB, Ethyl benzoate 1.39
DPGDB, Benzyl benzoate 1.30
DPGDB, Methyl benzoate 1.31
DPGDB, Ethyl-2-hydroxybenzoate 1.30
DPGDB, Diethylene glycol dibenzoate 1.32
DPGDB, Methyl-2-hydroxybenzoate 1.40
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DPGDB, DMSO 1.38

DPGDB, DMSO, Benzyl benzoate 1.33
DPGDB, DMSO, Methyl benzoate 1.39
DPGDB, DMSO, Methyl-2-hydroxybenzoate 1.40
DPGDB, DMSO, Ethyl-2-hydroxybenzoate 1.36
DPGDB, DMSO, Butyl benzoate 1.31
DPGDB, DMSO, Butyl benzyl phthalate 1.33
DPGDB, Methyl benzoate, Diphenyl isophthalate 1.39
DPGDB, Methyl benzoate, Butyl-4-hydroxybenzoate 1.30
DPGDB, Ethyl benzoate, Adiponitrile 1.32
DPGDB, Diethylene glycol dibenzoate, Methyl-2-hydroxybenzoate 1.35
DPGDB, Diethylene glycol dibenzoate, Methyl-2-hydroxybenzoate, DMSO 1.33
DPGDB, Diethylene glycol dibenzoate, Elhyl-2-hydroxybenzoate 1.31
DPGDB, Diethylene glycol dibenzoate, Ethyl-2-hydroxybenzoate, DMSO 1.34
DPGDB, Diphenyl isophthalate, Methyl-2-hydroxybenzoate 1.35
DPGDB, Diphenyl isophthalate, Ethyl-2-hydroxybenzoate 1.37

TABLE IV

Relative volatilities of m-xylene-o-xylene with mixtures containing sulfolane

Relative
Extractive distillation agent volatility

Sulfolane 1.30
Sulfolane, Diethylene glycol 1.32
Sulfolane, Dibutyl phthalate 1.32
Sulfolane, Adiponitrile, Acetophenone 1.34
Sulfolane, Adiponitrile, Nitrobenzene 1.36
Sulfolane, Adiponitrile, Maleic anhydride 1.32
Sulfolane, Adiponitrile, 1,4-Butanediol 1.30
Sulfolane, Adiponitrile, Ethyl benzoate 1.36
Sulfolane, DMSO, Benzyl alcohol 1.32
Sulfolane, DMSO, Dibutyl phthalate 1.34
Sulfolane, DMSO, Acetophenone 1.34
Sulfolane, DMSO, Nitrobenzene 1.34
Sulfolane, DMSO, Benzyl cyanide 1.33
Sulfolane, DMSO, Adiponitrile 1.32
Sulfolane, DMSO, Diethylene-glycol 1.33
Sulfolane, DMSO, Isophorone 1.31
Sulfolane, DMSO, Benzoic acid 1.30
Sulfolane, DMSO, Ethyl benzoate 1.34
Sulfolane, DMSO, Methyl benzoate 1.30
 154 L. BERG AND AN-I YEH
TABLE IV (Continued)

Relative
Extractive distillation agent volatility

Sulfolane, DMSO, Phenyl acetic acid 1.31

Sulfolane, DMSO, Adiponitrile, Ethyl benzoate 1.31
Sulfolane, Ethyl benzoate, Benzyl cyanide 1.31
Sulfolane, Maleic anhydride, Ethyl benzoate 1.31
Sulfolane, Maleic anhydride, Nitrobenzene 1.34
Sulfolane, Maleic anhydride, Ethylene carbonate 1.35
Sulfolane, Maleic anhydride, Propylene carbonate 1.31
Sulfolane, Maleic anhydride, Dimethylformamide 1.36
Sulfolane, Phthalic anhydride, DMSO 1.30
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Sulfolane, Phthalic anhydride, Ethylene carbonate 1.30

Sulfolane, Phthalic anhydride, Propylene carbonate 1.32
Sulfolane, Phthalic anhydride, Adiponitrile 1.31
Sulfolane, Ethyl benzoate, Diethylene glycol 1.31
Sulfolane, Ethylene carbonate 1.34
Sulfolane, Adiponitrile, Ethylene carbonate 1.33
Sulfolane, Adiponitrile, Propylene carbonate 1.30

effective. All of these possess a relative volatility in the range 1.30-1.39. Table III
presents a number of benzoates, all of which fall in the relative volatility range of
1.30-1.42. Table IV lists sulfolane and its mixtures which have a relative volatility
range of 1.30-1.36. Table V presents a number of chloro compounds, mostly
polychloro, having a relative volatility range of 1.30-1.69. Table VI lists
adiponitrile and its mixtures which have a relative volatility range of 1.30-1.38.
Table VII shows combinations of maleic anhydride and phthalic anhydride, all of
TABLE V

Relative volatilities of m-xylene-o-xylene with mixtures of chloro compounds

Relative
Extractive distillation agent volatility

2,3,4,6-Tetrachlorophenol,o-Dichlorobenzene 1.37
2,3,4,6-Tetrachlorophenol,2,4-Dichlorotoluene 1.39
2,3,4,6-Tetrachlorophenol, Dimethyltetrachloroterephthalate, 1.35
1,2,4,5· Tetrachlorobcnzene
2,3,4,6- Tetrachlorophenol, Dimethyltetrachloroterephthalate, 1.38
Ethylene glycol butyl ether
2,3,4,6-Tetrachlorophenol, 2,4·Dichlorotoluene, 1,2,3-Trichloro- 1.34
benzene
2,4,6·Trichlorophenol, Benzene hexachloride, 1,2,4-Trichlorobenzene 1.36
2,4,6·Trichlorophenol, Benzene hexachloride, 1,2,4,5·Tetrachloro· 1.37
benzene
1,2,4·Trichlorobenzene, o-Dichlorobenzene, Dioctyl phthalate 1.40
2,4,5-Trichlorophenol, Dimethyltetrachloroterephthalate, 1.46
Benzene hexachloride, o-Dichlorobenzene
2,4,5-Trichlorophenol, Benzene hexachloride, Dioctyl phthalate, 1.41
o-Dichlorobenzene
Pentachlorophenol, Dimethyltetrachloroterephthalate, 1.33
I,2,4-Trichlorobenzene, 0 -Dichlorobenzene
2,3,4,6-Tetrachlorophenol, p-Dichlorobenzene 1.38
 SEPN. OF m-XYLENE FROM a-XYLENE BY EXTR. DISTN. 155
TABLE V (Continued)

Relative
Extractive distillation agent volatility

Polychlorobenzene, 2,3,4,6-Telrachlorophenol, 1,2,4,5-Tetrachloro- 1.41

benzene, Trichloropropane
Dimethyltetrachloroterephthalate, Pentachlorophenol, o-dichloro- 1.43
benzene, 1,2,4-Trichlorobenzene
Dimethyltetrachloroterephthalate, I ,2,3-Trichlorobenzene, 1.48
o-Dichlorobenzene
2,3,4,6-Tetrachlorophenol, 1,2,3-Trichloropbenzene, 2,4-Dichloro- 1.41
toluene
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Dimethyltetrachloroterephthalate, 2,3,4,6-Tetrachlorophenol, 1.44

o-Dichlorobenzene
Dimethyltetrachloroterephthalate, 2,3,4,6-Tetrachlorophenol, 1.41
Ethylene glycol butyl ether
Dimethyltetrachloroterephthalate, 2,3,4,6-Tetrachlorophenol, 1.40
o-Dichlorobenzene
Dimethyltetrachloroterephthalate, 2,4,6-Trichlorophenol, Trichloro- 1.40
propane
Dimethyltetrachloroterephthalate, 2,4,6-Trichlorophenol, 1.42
1,2,4-Trichlorobenzene
Dimethyltetrachloroterephthalate, 2,4,6-Trichlorophenol, 1.39
Polychlorobenzene
Dimethyltetrachloroterephthalate, 2,4,6-Trichlorophenol, 1.49
2,4-Dichlorotoluene
Dimethyltetrachloroterephthalate, 2,4,6-Trichlorophenol, 1.41
2,6-Dichlorotoluene
2,4,6-Trichlorophenol, Benzene hexachloride, 1.2,4-Trichlorobenzene 1.43
Dimethyltetrachloroterephthalate, 2,4,6-Trichlorophenol, Benzene- 1.42
hexachloride, 2-Chlorotoluene
Dimethyltetrachlorotcrcphthalatc, 2,3,4,6-Tetrachlorophenol, 1.39
Benzene hexachloride, 2-Chlorotoluene
Dimethyltetrachloroterephthalate, 2,4,6-Trichlorophenol, Benzene- 1.42
hexachloride, Trichloropropane
Dimethyltetrachloroterephthalate, 2,4,5-Trichlorophenol, Benzene- 1.49
hexachloride, o-Dichlorobenzene
Dimethylletrachloroterephthalate, 2,4,5-Trichlorophenol, 1.38
Hexachlorobenzene, a-Dichlorobenzene
Dimethyltetrachloroterephthalate, 2,4,5-Trichlorophenol 1.43
Perchloropentacydohexane, a-Dichlorobenzene
2,4,5-Trichlorophenol, Benzene hexachloride, a-Dichlorobenzene, 1.39
Dihexyl phthalate
2,4,5-Trichlorophenol, Benzene hexachloride, o-Dichlorobenzene, 1.47
Dioctyl phthalate
2,4,5-Trichlorophenol, Polychlorobiphenyl, Tetrachlorophthalic 1.43
anhydride, a-Dichlorobenzene
2,4,6-Trichoorophenol, Polychlorobiphenyl, Tetrachlorophthalic 1.50
anhydride, o-Dichlorobenzene
2,3,4,6-Tetrachlorophenol, Polychlorobiphenyl, Tetrachloro- 1.39
phthalic anhydride, o-Dichlorobenzene
Pentachlorophenol, Polychlorobiphenyl, Tetrachlorophthalic 1.47
anhydride, o-Dichlorobenzene
Polychlorobiphenyl, Tetrachlorophthalic anhydride, o-Dichloro- 1.53
benzene
Polychlorobiphenyl, Tetrachlorophthalic anhydride, Trichloro- 1.42
propane
Polychlorobiphenyl, Tetrachlorophthalic anhydride, Polychloro- 1.40
benzene
 156 L. BERG AND AN-l YEH
TABLE V (Cantinued)

Relative
Extractive distillation agent volatility

2,4,5-Trichlorophenol, Tetrachlorophthalic anhydride, a-Dichloro- 1.49

benzene
2,3,4,6-Tetrachlorophenol, Tetrachlorophthalic anhydride, 1.39
a-Dichlorobenzene
2,4,5-Trichlorophenol, Tetrachlorophthalic anhydride, 1,2,4-Tri- 1.43
chlorobenzene
2,4,5-Trichlorophenol, Tetrachlorophthalic anhydride, p-Dichloro- 1.44
benzene
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2,4,5-Trichlorophenol, Tetrachlorophthalic anhydride, Polychloro- 1.53

biphenyl
2,4,5-Trichlorophenol, 1,1,1-Trichloro-2,2-bis(p-chlorophenyl)ethane, 1.43
Polychlorobiphenyl
2,4,5-Trichlorophenol, Tetrachlorophthalic anhydride, Dimethyl- 1.41
tetrachloroterephthalate
Dimethyltetrachloroterephthalate, Tetrachlorophthalic anhydride, 1.69
Polychlorobiphenyl, a-Dichlorobenzene
2,4,5-Trichlorophenol, Dimethyltetrachloroterephthalate, Polychloro- 1.41
biphenyl, a-Dichlorobenzene

TABLE VI

Relative volatilities of mixtures containing adiponitrile

Relative
Extractive distillation agents volatilities

Adiponitrile 1.34
Adiponitrile, DMSO 1.36
Adiponitrile, 1,4-Butanediol 1.32
Adiponitrile, Diethylene glycol 1.31
Adiponitrile, Dihexyl phthalate 1.30
Adiponitrile, Hydroquinone 1.33
Adiponitrile , Nitrobenzene 1.30
Adiponitrile, Tetraethylene glycol 1.35
Adiponitrile, Benzyl butyl phthalate 1.38
Adiponitrile, Methylp-hydroxybenzoate 1.32
Adiponitrile, Ethylene glycol phenyl ether 1.32
Adiponitrile, bis Phenol A 1.35
Adiponitrile, Benzyl alcohol 1.32
Adiponitrile, Butyl benzoate 1.37
Adiponitrile, Dimethyl phthalate 1.31
Adiponitrile, Diphenyl iosphthalate 1.37
Adiponitrile, Diethyl phthalate 1.35
Adiponitrile, Dihexyl phthalate 1.30
Adiponitrile, Tri isononyl rnellitate 1.31
Adiponitrile, Ethyl acetoacetale, Propylene glycol 1.30
Adiponitrile, Ethyl acetoacetate, 1,4-Butanediol 1.35
Adiponitrile, Ethyl acetoacetate, Diethylene glycol 1.37
Adiponitrile, Ethyl acetoacetate, DMSO 1.33
Adiponitrile, 1,4-Butanediol. DMSO 1.36
Adiponitrile, Methyl benzyl alcohol, Ethylene glycol phenyl ether 1.31
Adiponitrile, Butyl benzoate, Butyl benzyl phthalate 1.37
 SEPN. OF m-XYLENE FROM a-XYLENE BY EXTR. DISTN. 157
TABLE VI (Continued)

Relative
Extractive distillation agents volatilities

AdiponitriIe, DMSO, Diphenyl isophthalate 1.32

Adiponitrile, DMSO, Diethyl phthalate 1.31
AdiponitriIe, DMSO, Dihexyl phthalate 1.31
Adiponitrile, DMSO, Triisononyl mellitate 1.36
Adiponitrile, DMSO, Butyl cyclohexyl phthalate 1.33
Adiponitrile, DMSO, Butyl benzyl phthalate 1.36
Adiponitrile, Ethyl benzoate, Butyl benzyl phthalate 1.37
Adiponitrile, Nitrobenzene, bis Phenol A 1.30
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Adiponitrile, Ethylene carbonate, Dihexyl phthalate 1.33

Adiponitrile, Ethylene carbonate, Benzyl alcohol 1.31

TABLE VII

Relative volatilities of m-xylene-o-xylene with mixtures containing phthalic anhydride and maleic
anhydride

Relative
Extractive distillation agent volatility

Maleic anhydride 1.32

Phthalic anhydride, Ethyl benzoate 1.34
Phthalic anhydride, Propoxypropanol lAO
Phthalic anhydride, Maleic anhydride 1.31
Phthalic anhydride, Maleic anhydride, Dimethylsulfoxide 1.33
Phthalic anhydride, Maleic anhydride, Ethylacetoacetate 1.31
Phthalic anhydride, Maleic anhydride, Isobornyl acetate 1.33
Phthalic anhydride, Maleic anhydride, Adiponitrile 1.38
Phthalic anhydride, Maleic anhydride, Benzyl acetate 1.31
Phthalic anhydride, Maleic anhydride, Propoxypropanol 1.39
Phthalic anhydride, Maleic anhydride, Diethylene glycol methyl ether 1.32
Phthalic anhydride, Maleic anhydride, Sulfolane 1.36
Phthalic anhydride, Maleic anhydride, Dipropylene glycol 1.34
Phthalic anhydride, Maleic anhydride. Diethylene glycol 1.36
Phthalic anhydride, Maleic anhydride, Sulfolene 1.31
Phthalic anhydride, Maleic anhydride, Methyl sulfone 1.33
Phthalic anhydride, Maleic anhydride, Butyl benzyl phthalate 1.30
Phthalic anhydride, Maleic anhydride, Diethylene glycol diethyl ether 1.33
Phthalic anhydride, Maleic anhydride, Glycerol triacetate 1.35
Phthalic anhydride, Maleic anhydride, Phenyl acetate 1.35
Phthalic anhydride, Maleic anhydride, Methyl benzoate 1.32
Phthalic anhydride, Maleic anhydride, bis Phenol A 1.33
Phthalic anhydride, Maleic anhydride, Phenol 1.30
Phthalic anhydride, Maleic anhydride, 2-t-Butyl phenol 1.31
Phthalic anhydride, Maleic anhydride, o-sec. Butyl phenol 1.38
Phthalic anhydride, Maleic anhydride, 4-Nitrophenol 1.39
Phthalic anhydride, Maleic anhydride, m-Nitrobenzaldehyde 1.31
Phthalic anhydride, Maleic anhydride, Isobornyl methyl ether 1.35
Phthalic anhydride, Maleic anhydride, Catechol lAO
Phthalic anhydride, Maleic anhydride, 4-Nitrotoluene 1.39
Phthalic anhydride, Maleic anhydride, Ethylene glycol butyl ether lAO
Phthalic anhydride, Maleic anhydride, Diethyl maleate 1.32
Phthalic anhydride, Maleic anhydride, Benzaldehyde 1.33
 158 L. BERG AND AN-I YEH
TABLE VII (Continued)

Relative
Extractive distillation agent volatility

Phthalic anhydride, Maleic anhydride, o-Toluic acid 1.39

Phthalic anhydride, Maleic anhydride, Propionic anhydride 1.39
Phthalic anhydride, Maleic anhydride, Acetophenone 1.34
Phthalic anhydride, Maleic anhydride, Myristic acid 1.38
Phthalic anhydride, Maleic anhydride, 2-Ethyl hexyl acetate 1.34
Phthalic anhydride, Maleic anhydride, p-Ethyl benzaldehyde 1.39
Phthalic anhydride, Maleic anhydride, m-Nitrobenzoic acid 1.36
Maleic anhydride, Propoxypropanol 1.32
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Phthalic anhydride, Maleic anhydride, Hexyl acetate 1.30

Phthalic anhydride, Maleic anhydride, Butoxypropanol 1.33
Phthalic anhydride, Maleic anhydride, Ethylene glycol phenyl ether 1.30
Phthalic anhydride, Maleic anhydride, 1,4-Butanediol 1.30
Phthalic anhydride, Maleic anhydride, Propylene carbonate 1.30

TABLE VIll

Relative volatilities of m-xylene-o-xylene with mixtures containing dimethylformamide (DMFA)

Relative
Extractive distillation agent volatility

Dimethylformamide (DMFA) 1.33

Dimethylformamide (DMFA), Ethylene glycol 1.34
Dimethylformamide (DMFA), 1,4-Butanediol 1.32
Dimethylformamide (DMFA), 1,5-Pentanediol 1.31
Dimethylformamide (DMFA), Diethylene glycol 1.32
Dimethylformamide (DMFA), Triethylene glycol 1.32
Dimethylformamide (DMFA), Ethylene glycol phenyl ether
Dimethylformamide (DMFA), Adiponitrile, 1,4-butanediol 1.35
Dimethylformamide (DMFA), Adiponitrile , Dihexyl phthalate 1.34
Dimethylformamide (DMFA), Hydroquinone, m-Cresol 1.33
Dimethylformamide (DMFA), Hydroquinone, p-Cresol 1.33

TABLE IX

Relative volatilities of mixtures containing propoxypropanol

Relative
Extractive distillation agent volatility

Propoxypropanol, 1,4-Butanediol 1.35

Propoxypropanol, Propylene glycol 1.35
Propoxypropanol, 1,5-Pentanediol 1.31
Propoxypropanol, Hexylene glycol 1.35
Propoxypropanol, Diethylene glycol 1.38
 SEPN. OF m-XYLENE FROM o-XYLENE BY EXTR. DISTN. 159
TABLE X

Data from runs made in rectification column

- -

Column Wt.% of rn-xylene Relative

Agent type Overhead Bottoms volatility

Methyl benzoate Perforated plate 51.2 31.1 1.21

Ethyl benzoate 50.0 30.6 1.20
Benzyl benzoate 50.7 27.8 1.24
Dimethylsulfoxide 51.5 24.5 1.31
Maleic anhydride + Propoxypropanol 63 28 1.39
Adiponitrile 52.2 24.5 1.31
2,3,4,bTelrachlorophenol+ 62.7 27.0 1.40
2,4-Dichlorotoluene
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Methyl benzoate Packed 40.7 28.4 1.26

Ethyl benzoate 41.6 28.1 1.29
Notes: The feed mixture was 150gr. rn-xylene, 350gr. o-xylene. The agent was added at a rate of
20 ml/min. and 65'C. Total reflux was 5-10 mllmin.

which have a relative volatility in the range of 1.3-1.4. Table VIII lists several
combinations containing dimethylformamide which fall in the range 1.31-1.35
and Table I X lists five agents containing propoxypropanol with relative volatilities
in the range 1.31-1.38.
A few of the agents whose relative volatility had been determined in the
vapor-liquid equilibrium still were evaluated in both a plate and a packed
rectification column. The results are tabulated in Table X.
The worth of this separation can be judged by a cost comparison showing
mixed xylenes currently selling for 11 cents per pound, pure m-xylene at 36 cents
per pound and pure o-xylene at 12.5 cents per pound.

REFERENCES
Berg, L., "Separation of Benzene and Toluene from Non-aromatics", AIChE lournal, 29, # 6 , 962
(1983).
Berg, L., and Kober, P.J., "Ethylbenzene from Xylenes Using Polychloro Compounds", AIChE
lournal. 26. #5. 862 (1980).
Berg, L., "~tl;ylbknzene from ~ y i e n e sUsing Oxygenated Organic Compounds", AIChE lournol, 29,
#4, 694 (1983).