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Removal of benzene from

industrial wastewater by
vapor stripping
J. B. Phillips

a b

Department of Chemical Engineering ,

Tulane University , New Orleans, LA, 70118
b

Engineering Development Institute , 8627

North 106th Street, Milwaukee, WI, 53224
Published online: 15 Dec 2008.

To cite this article: J. B. Phillips (1995) Removal of benzene from industrial

wastewater by vapor stripping, Journal of Environmental Science and
Health . Part A: Environmental Science and Engineering and Toxicology, 30:5,
1075-1090, DOI: 10.1080/10934529509376250
To link to this article: http://dx.doi.org/10.1080/10934529509376250

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J. ENVIRON. SCI. HEALTH, A30(5), 1075-1090 (1995)

Removal of Benzene from Industrial

Wastewater by Vapor Stripping
J. B. Phillips*
Department of Chemical Engineering
Tulane University, New Orleans, LA 70118

Abstract
Four types of vapor stripping processes are designed in an effort to
investigate methods to treat industrial wastewater in compliance with
the Environmental Protection Agency's recently promulgated Benzene
National Emission Standards for Hazardous Air Pollutants (NESHAP)
regulations. Each vapor stripping technology involves a unit operation
producing a benzene-enriched vapor stream and a wastewater stream
containing less than 10 ppmw benzene, per the applicable regulation.
Steam stripping, vacuum stripping, air stripping, and natural gas stripping technologies are designed and evaluated. It is concluded that: (1)
steam stripping involves high operating costs due to the need to preheat
the feed; (2) vacuum stripping requires high capital investment because
of the number of equipment items needed; (3) air stripping provides only
a partial solution to the problem, as it converts a water pollution problem
into an air pollution problem which must be addressed; and (4) natural
gas stripping is the solution with fewest disadvantages of those examined,
and therefore is the recommended method.

* Until September 1995, address correspondence to: J.B. Phillips, Engineering Development
Institute, 8627 North 106th Street, Milwaukee, WI 53224.

1075
Copyright 1995 by Marcel Dekker, Inc.

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PHILLIPS

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Introduction
The Environmental Protection Agency's Benzene National Emission Standards for Hazardous Air Pollutants (NESHAP) Regulations (40 CFR Part
61) are spurring interest by manufacturers in the chemical, petrochemical,
and petroleum industries in novel technologies to treat produced water and
wastewater containing benzene [1]. Typically, benzene/water mixtures in such
facilities require two-stage treatment consisting of: (1) physical or chemical
means to reduce the benzene level to less than 10 ppmw in a confined environment, and (2) biological treatment prior to discharge to a river or other
waterway. Because biological treatment usually occurs in open ponds, the
initial physical or chemical treatment is necessary to prevent excessive evaporation of benzene into the air. Although the secondary biotreatment is an
important part of the pollution control process, this work will concentrate
on the initial treatment options required to reduce benzene concentration in
wastewater to below 10 ppmw.
All four methods examined herein represent technologies which have
recently begun to emerge and gain attention as promising candidates for
industrial-scale treatment. Initial studies have been conducted on a number
of treatment options which may be adequate to ensure compliance with the
applicable regulations. The experimental work which has been conducted to
date on the subject technologies allows the design and evaluation of equipment systems which can be put into industrial practice.
Steam stripping of benzene from an oil film is the subject of a study by
Brodskii, et al. [2]. The study concluded that the stripping rate from an oil film
was accelerated by 100-200% over that in a traditional bubble-cap tower, indicating that the stripping rate is strongly related to the surface area available
for mass transfer. The study also developed a mathematical model to describe
the performance of a thin oil film desorption unit, as it typically would operate in a coking plant. In addition to surface area, the benzene stripping rate
was found to be dependent on the oil temperature, pressure, and steam feed
rate. The dependence on surface area is the subject of a review by Huang [3].
Steam stripping also has been used to remove benzene and other pollutants from groundwater [4]. Solomon and Peterson demonstrated that benzene, toluene, ethylbenzene, xylene, trichloroethylene, pentachlorophenol,
and 1,2,4-trichlorobenzene can be removed from groundwater through the
use of steam stripping, although the steam-to-wastewater ratio is high. While
the issue of stability was not addressed by Solomon, it should be noted that

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VAPOR STRIPPING

1077

failure to preheat the groundwater can cause unstable operation of a steam

stripper. Other methods (i.e., alternatives to vapor stripping) for remediation of groundwater have been evaluated in significant detail, but each of the
better-known treatments has pronounced disadvantages [5].
Vacuum stripping of wastewaters also has been the result of some initial
experimental work. Khlevnoi, et al. [6] examined the flash vacuum stripping
of hot coking wastewaters. It was found that atmospheric emissions of aromatics were reduced, as were fixed nitrogen emissions. Moreover, the cooling which took place due to the evaporation process resulted in more efficient
operation of the downstream biotreatment process contained in the subject
system.
It has been demonstrated that air stripping can be used to remove benzene, toluene, w-xylene, /j-xylene, ethylbenzene, styrene, chlorobenzene, pdichlorobenzene, and 3-pentanone from wastewaters [7]. The specific technique used in the work is referred to as bubble column aeration, which allowed a unit operation approaching counter-current flow in that the air was
sparged into the bottom of the column, and the water samples were removed
from the water at the air injection point. The experimental setup allowed
calculation of Henry's Law constants:
y = K'x

(1)

where:
y solute concentration in the vapor phase in equilibrium with the solution,
g/L
x solute concentration in the solution, g/L
K Henry's Law constant (dimensionless)
For benzene, a Henry's Law constant of 0.222 was reported. In the same
work, increasing the ionic strength of the aqueous source phase was found to
increase the Henry's Law constant monotonically. The effect was likened to
a "salting out" phenomenon. Conversely, addition of alcohols to the aqueous
source phase was found to decrease the Henry's Law constants. The Henry's
Law constants for all of the nonpolar substances examined were of the same
order of magnitude, but the Henry's Law constant for 3-pentanone was about
two orders of magnitude lower due to the polar oxo group.
Related work examined air stripping for the removal of benzene and
other organics from water produced at offshore petroleum production platforms [8]. Benzene, toluene, butane, pentane, hexane, and cyclohexane were

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PHILLIPS

stripped from produced water by bubbling air through the water in a batch
process. The Henry's Law constants for several substances were reported
in this work, among these being a Henry's Law constant for benzene of
0.00549 atm m3/mol. When this is converted to a dimensionless Henry's
Law constant, as in the work by Harkins, et al. [7], a Henry's Law constant of
0.231 is obtained. This is in good agreement with the value of 0.222 reported
by Harkins. The study by Fang and Lin [8] considered two different sources
of organic pollutants in produced water: those found naturally as the water enters an offshore production platform, and those added at the platform
to facilitate operability. Substances in the latter category include methanol,
which is added as an antifreeze, and formic acid, which is used for its biocidic
properties. While air stripping was found to be effective in removing those
substances naturally present in produced water, it was not able to remove
methanol, formic acid, acetic acid, ethanol, or isopropanol which are added
to the produced water at the platform. It is clear that those substances which
are removed most easily are the nonpolar ones, whereas substances containing polar groups (hydroxyl or carboxyl) remain dissolved in the water. In this
respect air stripping can be considered to have similar operability prospects
as steam distillation [9].
Similar work on the use of air stripping to remove trace concentrations
of volatile organics, and aromatics in particular, from groundwater was conducted by McFarland [10]. It was found that air stripping can be an effective
means to reduce the level of aromatics such as benzene, toluene, and xylene
(BTX) in groundwater to below 10 ppb. Multiple air strippers in series were
able to reduce aromatics levels to below 1.0 ppb. The flow configuration in
this work was a packed tower, with groundwater being introduced at the top
of the column and the air inlet at the bottom of the column. Such a countercurrent flow operation allows the air-to-water ratio to be minimized. (It
should be noted that any vapor stripping technology can be operated with
countercurrent flow in order to minimize the vapor-to-liquid ratio.) Typical
design parameters given by McFarland are shown in Table 1.
As mentioned above, other technologies have been tested for their applicability to the removal of aromatics from wastewater. Schuckrow and
Pajak compared the efficacy of activated carbon adsorption, resin adsorption, biological treatment (both aerobic and anaerobic), and stripping [11].
Bench-scale testing of the technologies provided some valuable information
on which methods were the most promising. The results of their experiments indicated that granular activated carbon adsorption followed by ac-

VAPOR STRIPPING

1079

Table 1: Typical air stripper design parameters [10].

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Parameter
Col. diameter, cm (in)
Col. height, m (ft)
Packing height, m (ft)
Air-to-water ratio, by volume
Hydraulic loading rate,
L/min/m2 (GPMa/ft2)
Air loading rate,
Std. m3/min/m2 (SCFM6/ft2)
a

Recom. min.

Recom. max.

10.0 (4.0)
3.5(12)
2.5 (8.0)
50:1

48 (18)
6.0 (20)
4.5 (15)
250:1

200 (5.0)

1200 (30)

30 (100)

150 (500)

GPM: gallons per minute.

SCFM: standard cubic feet per minute.

tivated sludge treatment can achieve nearly complete removal of aromatics.

Unfortunately, sustained removal of aromatics could not be effected under
continuous operation. Similar operability problems were experienced by Selvakumar and Hsieh [12] in experiments conducted on adsorption of aromatics by biomass. These researchers found that although an inert microbial
biomass secondary sludge can adsorb aromatics initially, and that the adsorption follows the Freundlich isotherm, in time the sludge will release aromatics into soil and groundwater, thereby preventing landfarm application.
Activated carbon treatment of wastewater containing aromatics can be effective [13], but high loadings or high volumes of processed wastewater that
would be typically found in an industrial operation make such an alternative
cost-prohibitive. Thus, it can be argued by default that vapor stripping is the
most promising alternative for the treatment of industrial wastewater containing aromatics such as benzene.
The remainder of this work concentrates on the design of equipment systems to implement the aforementioned four vapor-stripping technologiessteam stripping, vacuum stripping, air stripping, and natural gas stripping.
The advantages and disadvantages of each variety of stripping process are
evaluated, and a preliminary economic analysis of each process is conducted.

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PHILLIPS

Design Methodology

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A. Steam Stripping
For the design of steam stripping systems, a process simulator was employed
(ChemCAD II, Chemstations Software). The flash drum unit operation was
used to model a single-stage stripping process. For steam stripping, feeds to
the flash drum consisted of a water stream containing up to 1700 ppm benzene, and steam. For all stripping operations examined, an upper limit of
1700 ppm for the benzene content of the wastewater stream was chosen because this value represents the solubility limit of benzene in water at ambient
conditions. If, in the field, the wastewater contained more than 1700 ppm
benzene, the excess could be removed by phase separation (i.e., skimming).
The flash drum and any feed to it were specified to be at ambient pressure
(1.0 atm). In the case of steam stripping, the feed temperature was 310 K
(100F) for the wastewater stream and 373 K (212F) for the steam. Steam
stripping could be conducted either in a single-stage operation, such as a
flash drum, or in a multistage (i.e., packed) tower, with steam being added
at the bottom of the tower and wastewater being introduced at the top. Multistage contacting typically allows the requisite separation to be performed
while minimizing the vaponliquid ratio. The single-stage and multistage contacting configurations for steam stripping are shown in Figure 1.
B. Vacuum Stripping
The ChemCAD II process simulator also was employed to design vacuum
stripping systems. The key parameter which determines the separation efficacy of a vacuum stripping system is the pressure. Ambient temperature and
adiabatic operating conditions are specified, with changes in pressure causing
changes in the amounts of liquid and vapor product, and differing compositions of the products. As in the design of steam stripping systems, a flash drum
unit operation can be used to predict the performance of a single-stage contacting operation, and a packed tower can be used to evaluate any improvement in performance that multistage contacting would produce. In contrast
to steam stripping, vacuum stripping only requires one feed (the wastewater
stream) to the flash drum (or tower). If a packed tower is used, the wastewater
feed is at the top stage. The single-stage and multistage contacting configurations for vacuum stripping are shown in Figure 2.

1081

VAPOR STRIPPING
O/W Separator
Condenser

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Benzene

Water/
Benzene
Water
(Benzene-saturated)

Steam Stripper
Steam

Clean Water
(<10 ppm Benzene)

Figure 1: Schematic of steam strippingprocess.

C. Air Stripping and Natural Gas Stripping

Laboratory data provided by Harkins, et al. [7] and Fang and Lin [8] allowed
air stripping processes to be designed with a higher confidence level than designs based solely on simulated data. The Henry's Law constant for benzene
was employed to determine the liquid:vapor ratio required to perform the

1082

PHILLIPS
Condenser

O/W Separator

Vacuum Pump
-10kPa

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Benzene

Water/
Benzene
Water
(Benzene-saturated)

Vacuum Stripper

Clean Water
(<10 ppm Benzene)

Figure 2: Schematic of vacuum stripping process.

separation. For air stripping or natural gas stripping, it is possible to remove

benzene in a single stage by bubbling the vapor into a tank containing wastewater, or in a multistage operation by introducing the wastewater into the top
of a packed tower and connecting the vapor inlet to the bottom of the tower.
The single-stage and multistage contacting operations for air stripping and
natural gas stripping are shown in Figure 3.

1083

VAPOR STRIPPING

Benzene Vapor in
Air or NG

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Water/Benzene

oO
Air or NG

o o
ITT!

Clean
Water

Clean Water
(<10 ppm Benzene)

Figure 3: Schematic of air stripping and natural gas stripping processes

(single-stage contacting, right; multistage contacting, left).

Results
In general, it is recognized that multistage contacting operations are more
efficient than single-stage operations and are cheaper to operate. However,
near-term compliance with applicable regulations may dictate the level of sophistication which operating companies can afford to consider. Accordingly,
the remainder of this work will concentrate on the design of single-stage systems.

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PHILLIPS

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A. Steam Stripping
The wastewater feed to the steam stripper contained between 50 ppm and
1700 ppm benzene. (The 50 ppm figure was based on a case study.) Varying amounts of steam were added, and the concentration of benzene in the
liquid product stream was examined. It was anticipated that progressively
increasing the steam-to-wastewater ratio on the input to the stripper would
result in a monotonic decrease in the benzene content of the liquid effluent.
However, the process simulator predicted unstable operation of the stripping
unit unless the wastewater was preheated to near its boiling point. Preheating was judged to be uneconomical, because of the capital costs associated
with installing a preheater, as well as the operating costs involving the input
of considerable energy into a wastewater stream. Thus, further investigation
into steam stripping was not pursued.

B. Vacuum Stripping
Initial simulations of vacuum stripping systems concentrated on the removal
of benzene from a wastewater stream containing 50 ppm benzene. Using a
single-stage separation system, the pressure in the flash drum was varied until
the effluent liquid stream contained less than 10 ppm benzene. This occurred
at a pressure of about 9 kPa (slightly less than 1.5 psia). The relationship between flash drum pressure and liquid effluent benzene concentration is shown
in Figure 4. It is observed that the level of benzene in the liquid effluent is a
strong function of flash pressure, decreasing monotonically with decreasing
pressure.
The fraction of benzene removed from the subject wastewater stream is
also strongly a function of pressure. Figure 5 shows that the percent benzene
removed initially increases rapidly with pressure reductions from 9.65 kPa
down to approximately 9.0 kPa, whereas additional benzene removal requires
more drastic pressure reductions. As benzene removal approaches the 8090% range, the water-to-benzene ratio in the overhead stream is seen to increase dramatically (Figure 5). Reducing the benzene content in the subject wastewater stream to 10 ppm will result in an overhead stream water-tobenzene ratio of approximately 20, and additional reductions in the benzene
content of the wastewater stream result in even higher overhead water loads.
This is significant because the overhead processing equipment must be sized
to handle the vapor loads for both water and benzene. (See Figure 2.)
Capital costs for vacuum stripping are anticipated to be high. In addition to a stripping tower or flash drum, an overhead condenser and vacuum

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8.250

8.500

8.750

9.000

9.250

9.500

9.750

Pressure (kPa)
Figure 4: Effect of pressure on liquid effluent benzene level in a vacuum stripping process (dashed line indicates 10 ppm regulatory threshold).

80-

Kg
4)

^\^

Percent Benzene
Removed from
Wastewater

60-

40-

\
20o

08.250

Water/Benzene Ratio

8.500

8.750

-* .

9.000

9.250

9.500

9.750

Pressure (kPa)

Figure 5: Effect of pressure on benzene removal, and on overhead water-tobenzene ratio in a vacuum stripping process.

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PHILLIPS

pump are needed. Both of these equipment items must be sized to process
the total vapor flow. In particular, sizing a vacuum pump to handle a benzene
vapor and water vapor stream in which the benzene vapor is only-5% of the
total (Figure 5) will cost about six times as much as a unit which only would
need to process the benzene vapor. (Based on the power law cost estimation method discussed and analyzed by Garnett and Patience [14].) Due to
the high associated capital costs which are expected to be incurred up front,
further investigation into the design of vacuum stripping systems was not pursued.

C. Air Stripping and Natural Gas Stripping

The experimental data reported by Harkins, et al. [7], and Fang and Lin [8]
allowed calculation of vapor-to-liquid ratios for air stripping and natural gas
stripping to specified target values. Using a wastewater feed stream containing 1700 ppm benzene (the saturation limit), effluent benzene levels were
calculated as a function of the inlet vapor-to-liquid ratio. The results, shown
in Figure 6, indicate that a molar vapor-to-liquid ratio of approximately 0.57:1
will result in an effluent benzene level of 10 ppm. (Conversion to units commonly used in industrial operations yields a volumetric ratio of just over
100 SCFM gas per GPM liquid.) While it is expected that there would be
different mass ratios for air stripping vs. natural gas stripping, the volumetric
ratios and the molar ratios should be the same for the two methods.
This leaves the question of whether to specify air stripping or natural gas
stripping as the technology of choice for removing benzene from industrial
wastewater. A number of factors need to be considered in making this decision. In air stripping operations, the expected products would be (relatively)
clean wastewater and an air-in-benzene mixture. Treatment of the air-inbenzene mixture can be problematic. In essence, air stripping has converted a
water pollution problem into an air pollution problem. One possibility would
be to pass the vapor through carbon canisters [13], but there are a number
of disadvantages to this approach. First, the cost can be high, because the
benzene-to-carboh ratio must be kept low in order to prevent benzene breakthrough. Beyond that, the carbon canisters must be regenerated periodically.
If this is done with steam, then the steam must be condensed and treated. Air
emissions of benzene also can result from the regeneration process. At best,
it can be concluded that air stripping provides only a partial solution to the
problem at hand.

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VAPOR STRIPPING

200.0
1.000-
o

-150.0
a
DC

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100.0

50.0

20

40

60

80

100

Benzene Level in the Aqueous Phase (ppm)

Figure 6: Relationship between inlet vapor-to-liquid ratio and liquid effluent

benzene level (dashed line indicates 10 ppm regulatory threshold).

Moreover, there is a safety concern associated with air stripping. If the

contaminatedwastewater contains significant concentrations of other volatile
organics, the vapor effluent may be explosive. Because air stripping is not
inherently safe, alternatives should be given due consideration.
Natural gas stripping does not possess any of the aforementioned disadvantages associated with air stripping. Effluents from a natural gas stripping
process are the clean wastewater and natural gas which contains benzene.
If the stripping is conducted with natural gas which was designated for fuel
purposes, then the benzene would be combusted along with the natural gas.
Thus, natural gas stripping provides a complete solution to the benzene problem, because the benzene is converted to carbon dioxide along with the natural gas.
In addition, natural gas stripping does not produce potentially explosive
mixtures of air and hydrocarbons, as might arise during the operation of an air
stripping process. If the decision to operate an air stripping process was made,
one use of the vapor effluent might be as the oxidant for a boiler or equivalent

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PHILLIPS

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fuel-burning system. While this would result in conversion of stripped benzene to carbon dioxide, it does not address the explosion issue. In contrast,
natural gas stripping produces a vapor effluent which is above the upper explosion limit, and which remains so until it is introduced into a combustion
chamber with oxidant (i.e., air).

Conclusions
Steam stripping, vacuum stripping, air stripping, and natural gas stripping systems have been designed for the removal of benzene from industrial wastewater.
Steam stripping is likely to be of greatest use when preheating the wastewater is not required (i.e., stripping benzene from hot wastewaters). However,
the unfavorable economics of preheating the wastewater suggest that steam
stripping usually will not be the method of choice.
Vacuum stripping may be most effective when stripping only small quantities of benzene is needed. Unfortunately, as the amount of benzene and water vapor produced in a vacuum stripping unit increase, so do the costs of the
overhead equipment. This factor becomes pronounced as the benzene level
in the wastewater is reduced and the water-to-benzene ratio in the overheads
is increased. Thus, capital cost considerations suggest that vacuum stripping
also will not be the technology of choice.
Air stripping and natural gas stripping can be accomplished simply and
effectively; both methods can reduce the benzene level in wastewater to under
10 ppm. A molar vapor-to-liquid ratio of 0.57 is required in either case. Air
stripping is disfavored because it merely converts a water pollution problem
into an air pollution problem, and because it produces a potentially explosive
mixture inside the stripping equipment. Neither of these disadvantages is
associated with natural gas stripping. The results of this work suggest that
natural gas stripping is the technology of choice for removing benzene from
industrial wastewater.

Notation
BTX
GPM
NESHAP
SCFM

benzene, toluene, and xylene

gallons per minute
National Emission Standards for Hazardous Air Pollutants
standard cubic feet per minute

VAPOR STRIPPING
K
x
y

1089

Henry's Law constant

benzene level in the liquid phase
benzene level in the vapor phase

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References
[1] United States Environmental Protection Agency. National emission
standards for hazardous air pollutants; benzene waste operations; final
rule; 40 CFR 61. Federal Register, 58(4):3072-3105,1993.
[2] E. V Brodskii, S. V. Gudimenko, and N. I. Potemkina. Height of transfer
unit in the desorption of benzene hydrocarbons from absorption oil in
film apparatus. Metall. Koksokhim., 73:94-97,1981.
[3] H. T. Huang. Environmental-pollution surface chemistry. Chieh Mien
Hua Hsueh Hui Hsin, 1(3):2-6,1981.
[4] R. L. Solomon and D. J. Peterson. An innovative solution for steam
stripping of volatile organic components and high boiling pollutants
from groundwaters with the aquadetox stripping system. In Proc. of the
48th International Water Conf., pages 310-315. 1987.
[5] P. A. Hajali and L. W. Canter. Rehabilitation of Polluted Aquifers.
NCGWR 80-12, National Center for Ground Water Research, 1980.
[6] I. S. Khlevnoi, V. A. Chimarov, A. L. Shtein, A. V. Popov, V G. Gorshkov, and A. I. Bogdanov. Cooling of wastewaters. KoksKhim., 1:4546,1988.
[7] B. Harkins, T. L. Boehm, and D. J. Wilson. Removal of refractory organics by aeration. VIII. Air stripping of benzene derivatives. Sep. Sci.
Technol., 23(l-3):91-104, 1988.
[8] C. S. Fang and J. H. Liri. Air stripping for the treatment of produced
water. J. Pet. Technol, May:619-624, 1988.
[9] R. Adams, J. R. Johnson, and C. F. Wilcox. Laboratory Experiments in
Organic Chemistry, pages 60-66. Macmillan, New York, 1970.
[10] W. McFarland. Air stripping removes petroleum from groundwater. Water/Engrg. Mgmt., May:48-52, 1989.
[11] A. J. Schuckrow and A. P. Pajak. Bench scale assessment of concentration technologies for hazardous aqueous waste treatment. In Land Disposal: Hazardous Waste, Proc. Annu. Res., PB81-173882, pages 341-351.
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[12] A. Selvakumar and H. N. Hsieh. Adsorption of organic compounds by

microbial biomass. Int. J. Environ. Stud., 30(4):313-319, 1987.
[13] A. Yoshihara, T. Yoshihara, K. Okata, and S. Sakaguchi. Activated carbon for water treatment. Japan, 71 25,490 (cl. C 01b), 23 Jul 1971, Appl.
62 34,044, 1972.
[14] D. I. Garnett and G. S. Patience. Why do scale-up power laws work?
Chem. Eng. Prog., 89(8) :76-78, 1993.

Received: November 1, 1993

Accepted: April 16, 1994