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Solvent extraction of phenol with cumene from

wastewater
a
Junteng Liu , Jing Xie , Zhongqi Ren & Weidong Zhang
a
State Key Laboratory of Chemical Resource Engineering, Beijing Key Laboratory of
Membrane Science and Technology , Beijing University of Chemical Technology , P.O. Box
1#, No. 15, N. 3rd Ring Rd East, Beijing , 100029 , China Phone: Tel. +86 10 6442 3628 Fax:
Tel. +86 10 6442 3628
Published online: 20 May 2013.

To cite this article: Junteng Liu , Jing Xie , Zhongqi Ren & Weidong Zhang (2013) Solvent extraction of phenol with cumene
from wastewater, Desalination and Water Treatment, 51:19-21, 3826-3831, DOI: 10.1080/19443994.2013.796993

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 Desalination and Water Treatment 51 (2013) 3826–3831
www.deswater.com May

doi: 10.1080/19443994.2013.796993

Solvent extraction of phenol with cumene from wastewater

Junteng Liu, Jing Xie, Zhongqi Ren, Weidong Zhang*

State Key Laboratory of Chemical Resource Engineering, Beijing Key Laboratory of Membrane Science and
Technology, Beijing University of Chemical Technology, P.O. Box 1#, No. 15, N. 3rd Ring Rd East, Beijing
100029, China
Tel. +86 10 6442 3628; Fax: +86 10 6443 6781; email: zhangwd@mail.buct.edu.cn
Downloaded by [Uppsala universitetsbibliotek] at 18:21 04 October 2014

Received 8 August 2012; Accepted 10 April 2013

ABSTRACT

In this paper, the extraction of phenol from wastewater using cumene as an extractant is
investigated. H2SO4 and HCl are used for the pH adjustment of the wastewater. The effects
of extraction temperature, pH value, initial concentration, and phase ratio on the extraction
performance are studied. The results show that the distribution coefficient D increases with
the increase in extraction temperature (from 25 to 55˚C) and the decrease in pH value of the
aqueous phase (from 13.0 to 0.0). The type of the acids and the initial concentration of
phenol show a weak effect on the distribution coefficient. The stripping of loaded organic
and the reuse of extractant are also discussed.

Keywords: Phenol; Solvent extraction; Cumene

1. Introduction hazardous character [4]. Both, US Environmental

Protection Agency and European Union regard phenol
Phenol is a widely used commodity chemical in
as hazardous substance that is discharged into the
manufacturing process, such as synthetic resins, plas-
aquatic environments.
tics, pharmaceuticals, intermediate of dyes, etc. Since
Several techniques have been developed to
1952, the three-step Hock process (also called cumene
dephenolize the wastewater, such as solvent extraction
peroxidation method) is the main commercial process
[5], biological treatment [6], pyrolytic method [7],
for the production of phenol, which consists of three
adsorption [8,9], and membrane separation [10,11].
steps [1–3]: (1) reaction of benzene with propylene to
Among them, solvent extraction is the most effective
produce cumene; (2) oxidization of cumene with air to
method to remove and recover phenol from the
produce cumene hydroperoxide; and (3) decomposi-
wastewater. Many extractants have been applied to
tion of cumene hydroperoxide with an acid to
the extraction of phenol and show excellent extraction
produce phenol along with acetone as a byproduct. A
performance, such as octanol [4], N-octanoylpyrroli-
large amount of phenol wastewater is produced in
dine [12], amines [5], Cyanex 923 [13], diethyl carbon-
this production process, which leads to a serious
ate [14], MIBK [15], TBP [16], and ionic liquids [17],
environmental problem because of its highly toxic and
etc. As cumene is the intermediate material in
*Corresponding author. cumene–phenol process, which can be circulated in

Presented at the 2012 Qingdao International Desalination Conference June 26–29, 2012, Qingdao, China

1944-3994/1944-3986 Ó 2013 Balaban Desalination Publications. All rights reserved.

 J. Liu et al. / Desalination and Water Treatment 51 (2013) 3826–3831 3827

the whole process, the reuse of cumene will not the bottom layer for phenol concentration analyses.
induce secondary pollutants. Besides, cumene shows The phenol concentration in the extractant is calcu-
many advantages as an extractant in terms of its low lated by mass balance. After extraction, the loaded
cost, low solubility, and excellent chemical stability. organic phase is stripped with 0.1 mol L
1 of NaOH
Consequently, cumene is the most widely used solution, and then the regenerated extractant is used
extractant in industry. It is of good importance to for following cycles of extraction and stripping tests.
investigate its extraction performance systemically for All the stripping experiments are carried out using
design and optimization of a solvent extraction the same procedure and conditions as the extraction
process. experiments.
Using cumene as an extractant, the extraction of The phenol concentration in the aqueous solution
phenol from wastewater is investigated in this paper. and the stripping reagent is measured by a UV-vis
The following factors are considered, including pH spectrophotometer setting the absorption wavelength
value of the phenol solution, type of the inorganic at 510 nm and 4-amino antipyrine (4-AAP) used as the
acid used to adjust the pH of the feed phase, phenol indicator. The pH value of the aqueous phase is
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initial concentration, phase ratio, and extraction determined with a pH meter (PXS-450 model) with a
temperature. Furthermore, the stripping and reuse of deviation of ± 0.01. Each experiment is repeated three
the extractant are also investigated. times under each operating condition, and the results
from same experiment agree with 5%.
The results are expressed as phase ratio a,
2. Materials and methods distribution coefficient D, extraction efficiency E, and
stripping efficiency R defined as
2.1. Chemicals and solutions
Ve
The chemicals used in this work, include C6H5OH a¼ ð1Þ
Vp
(>99.0%), NaOH (>96.0%), H2SO4 (95%–98%), HCl
(36%–38%), cumene (>98.5%), 4-amino antipyrine
(>99.0%), and potassium hexacyanoferrate (>99.0%). Ce;eq
D¼ ð2Þ
All these chemicals are analytically pure and used Cp;eq
without further purification. Physical properties of
cumene and phenol are listed in Table 1. The simu-
Cp;ini
Ce;eq
lated phenol wastewater is prepared with deionized E¼  100% ð3Þ
water and weighed amount of phenol. The pH is Cp;ini
adjusted to a desired value by adding different type
of acids (H2SO4, HCl). Solutions of 0.1–1.0 mol/L Cs;eq
sodium hydroxide are used as stripping reagents. S¼  100% ð4Þ
Ce;ini

where C and V are the concentration (mg/L) and the

2.2. Experiments volume (ml), the subscripts p, e, s, eq, and ini repre-
Known volumes of extractant and phenol solution sent the phenol solution, extractant, and stripping
are shaken mechanically in a constant-temperature reagent at equilibrium and initial state, respectively.
water bath with a vibrating rate of 200 rpm at the
selected temperature for an appropriate time period.
Then, the samples are allowed to stand for 20 min for
3. Results and discussion
phase separation. The faffinate sample is taken from
3.1. Effect of the extraction time
Table 1 The effect of the extraction time on distribution
Physical properties of the pure compounds
coefficient D is considered, and the results are shown
Chemical Cumene Phenol in Fig. 1. The operation condition is 100 ppm and pH
value 7 of phenol solution at 25˚C. As shown in Fig. 1,
Formula C6H5C3H5 C6H5OH
the extraction efficiency remains constant after 20 min.
Relative molecular 120.2 94.1
These results indicate that the time required to
Boiling point, ˚C 152.4 182
achieve the extraction equilibrium is less than 30 min.
Flashing point 31 –
So, 30 min is selected for the extraction in the
Relative density 0.86 1.07
following experiments.
 3828 J. Liu et al. / Desalination and Water Treatment 51 (2013) 3826–3831

100% 2.0

H2SO4
80%

Distribution coefficient D
HCl
Extraction efficiency E

1.5

60%
1.0
40%

0.5
20%

0% 0.0
0 10 20 30 40 50 0 1 2 3 4 5 6 7
Extraction time (minutes) pH value of the wastewater
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Fig. 1. Effect of time on the extraction of phenol from Fig. 2. Extraction of phenol from different inorganic acid
aqueous solution at 298.3 K; pH = 7; Cp,ini = 100 ppm. aqueous phases using cumene at 298.3 K; Cp,ini = 100 ppm.

3.2. Effect of the inorganic acid Table 2

Effect of pH value on the extraction of phenol from H2SO4
HCl and H2SO4 are used to adjust acidity of the aqueous solution at 298.3 K
phenol aqueous solution. No significant change on the pH Cp,ini/ppm Cp,eq/ppm Ce,ini i/ppm D E/%
distribution coefficient D is found from the results
shown in Fig. 2. This fact ascertains that the effect of 0 100 40.97 59.03 1.45 59.22
the kind of inorganic acid on the extraction can be 1 100 45.26 54.74 1.22 54.95
ignored. Because of its non-volatility, H2SO4 is usually 3 100 45.60 54.4 1.20 54.61
selected for the pH adjustment of the phenol solution 5 100 45.77 54.23 1.19 54.44
in industries. 7 100 45.77 54.23 1.19 54.44
9 100 46.80 53.2 1.15 53.41
10 100 61.89 38.11 0.62 38.39
3.3. Effect of the pH value 11 100 95.34 4.66 0.05 5.10
The effect of the pH value of the phenol solution 12 100 96.37 3.63 0.04 4.07
on extraction behavior is investigated by adjusting a 13 100 96.54 3.46 0.04 3.90
100 ppm phenol solution to the desired pH by the
addition of H2SO4. The results are listed in Table 2
and Fig. 3. It is shown that the extraction performance 1.6 100
strongly depends on the pH value of the phenol solu-
tion. From 0 to 9.0 of the pH, phenol is effectively 80
Distribution coefficient D

extracted from the aqueous solution and the pH value 1.2 Extraction efficiency E
has a small effect on the distribution coefficient D.
60
The distribution coefficient and the extraction effi-
0.8
ciency reach maximum of 1.45 and 59.2%, respec-
tively. However, the distribution coefficient, D, 40

decreases sharply from 1.15 to a minimum value of

0.4
0.04 when pH value is kept increasing to 13.0. These 20
results agree with similar work on the extraction of
phenol with MIBK (methyl isobutyl ketone) from the 0.0 0
coal gasification [18]. Li et al. also found that the 0 2 4 6 8 10 12 14
pH value of the wastewater
distribution coefficient for phenol extracted with
N-octanoylpyrrolidine begins to drop at pH > 8, and Fig. 3. Effect of pH value on the extraction of phenol from
little phenol can be extracted at pH > 12 [12]. H2SO4 aqueous solution at 298.3 K, Cp,ini = 100 ppm.
This deterioration of the extraction performance
can be explained by phenol-ionization at a high pH efficiency decreases greatly due to phenol’s dissocia-
value. The acidic dissociation constant of phenol pKa tion. Therefore, to ensure the phenol removal
is 10. When pH becomes higher than 9, the extraction efficiency in practical application, the pH value of the
 J. Liu et al. / Desalination and Water Treatment 51 (2013) 3826–3831 3829

phenol solution should be adjusted and the best 100.0

pH value should be kept at neutral or weak acid
considering the operating cost. 80.0

Extraction efficiency E
60.0
3.4. Effects of the phenol initial concentration
50ppm
The phenol initial concentration of the aqueous 40.0
100ppm
phase ranges between 50 and 5,000 ppm and the pH
200ppm
value are fixed at 1 or 7. The results reported in Fig. 4
20.0
show the relationship between the initial phenol 2167ppm

concentration and the distribution coefficient, D. The

0.0
distribution coefficient is independent of the initial 0 1 2 3 4 5
concentration and pH value under this experimental Phase ratio
condition.
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Fig. 5. Effect of phase ratio on the distribution coefficient,

D, of phenol from phenol aqueous solution at 298.3 K.
3.5. Effects of the phase ratio
In this work, the extraction of phenol between of distribution coefficient D vs. temperature is
water and solvent is measured over a range of initial depicted in Fig. 6. The distribution coefficient D
phenol concentrations from 50 ppm to 2,167 ppm at a increases with the increase of temperature, indepen-
phase ratio between 0.5 and 4.0. The results are shown dent of the initial concentration of phenol. The linear
in Fig. 5. The extraction efficiency, E, increases with relation between distribution coefficient D and
the increase of the phase ratio and higher phase ratio temperature is found to be as described in Eq. (5).
will facilitate the extraction performance. The separa-
tion of phenol relies on its different solubility in D ¼ 7:2  10
3 T
0:9878 ð5Þ
extractant and water. Higher phase ratio means more
extractant in unit volume of the phenol solution,
which significantly enhances the cumene extraction
capability. Therefore, the degree of extraction for phe- 3.7. The stripping and reuse of extractant
nol can be improved with the addition of the cumene. In industry, it is of important to reuse the extract-
ant without significant loss in extraction ability.
Cumene-free phenol is required to recycle for the use
3.6. Effects of the temperature
of extraction. For the assessment of recycling behavior
At a constant phase ratio of one, the effect of the of cumene, the feed aqueous phase is equilibrated
temperature on extraction process is studied. The plot with the organic phase at 1:1 phase ratio. Sodium

2.0 1.5

pH=1
100ppm
1.6 1.4
Distribution coefficient D

pH=7
1000ppm
Distribution coefficient D

1.2 1.3

0.8 1.2

0.4 1.1

0.0 1.0
10 100 1000 10000 290 300 310 320 330 340
Phenol initial concentration in wastewater (ppm) Extraction temperature (K)

Fig. 4. Effects of the initial concentration of phenol from Fig. 6. D vs. T for the extraction of phenol by cumene
H2SO4 aqueous solution at 298.3 K. from aqueous solution at various initial concentrations.
 3830 J. Liu et al. / Desalination and Water Treatment 51 (2013) 3826–3831

Table 3 shows excellent extraction performance on phenol in

Effect of NaOH concentration on stripping of phenol from acidic solution. The extraction efficiency has slight
loaded organic at 298.3 K difference between H2SO4 and HCl for pH value
CNaOH/mol L
1 Ce,ini/ppm Cs,eq/ppm S adjustment. Cumene has an excellent extraction capa-
bility on phenol. When 0.1 mol/L NaOH is used for
0 1169.53 627.27 53.63
stripping of phenol from loaded cumene, the stripping
0.1 1169.53 1165.85 99.68
efficiency is above 99% under the current experimen-
0.5 1169.53 1169.28 99.98
tal conditions.
1.0 1169.53 1169.28 99.98
Acknowledgements
We gratefully acknowledge the financial support
1.6 for this project from the National Natural Science Foun-
dation of China (Nos. 21006001 and 21076012) and the
Research Fund for the Doctoral Program of Higher
Distribution coefficient D

1.2 Education (Nos. 200800100001 and 20100010120001).

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