Journal of Membrane Science 452 (2014) 426432

Contents lists available at ScienceDirect

Journal of Membrane Science

journal homepage: www.elsevier.com/locate/memsci

Membrane-assisted VOC removal from aqueous acrylic latex

Bridget Ulrich a, Timothy C. Frank a,b, Alon McCormick a, E.L. Cussler a,n
a
b

Chemical Engineering and Materials Science, University of Minnesota, Minneapolis, MN 55455, USA
Engineering & Process Science Laboratory, The Dow Chemical Company, Midland, MI 48667, USA

art ic l e i nf o

a b s t r a c t

Article history:
Received 4 March 2013
Received in revised form
11 October 2013
Accepted 12 October 2013
Available online 23 October 2013

Volatile organic compounds (VOCs) in model aqueous solutions and in acrylic latex binder used for
formulating latex paint can be stripped without foaming by using a nanoporous hydrophobic polypropylene
membrane. The stripping gas employed was dry, room temperature nitrogen or 50 1C water-saturated air. For
the dry nitrogen stripping gas, fouling was minimal for the hydrophobic polypropylene over several days, in
sharp contrast to experiments with hydrophilic membranes. No fouling of the polypropylene membrane was
observed for experiments with the water-saturated strip gas. The rate of VOC removal in these experiments
depends on mass transfer in the aqueous latex and in the membrane. These results allow estimates of the
membrane area to strip VOCs from commercially relevant quantities of acrylic latex paint.
& 2013 Elsevier B.V. All rights reserved.

Keywords:
Latex paint
Volatile organic compounds
Porous membranes

1. Introduction
Latex paint has an odor. When a consumer enters a freshly
painted room, he or she will not only notice the color and
smoothness of the painted surfaces, but also the smell. This smell
has been described as chemical or like vodka. Most consumers
do not like this smell; it causes headaches for some consumers.
While the smell is usually ushed from a well-ventilated room in a
day or so, it is still undesirable. Odor-free latex paint would be
regarded as superior [1,2].
Ironically, the smell in latex paint is due to trace amounts of volatile
organic compounds that are not essential to the paint's function. For
typical acrylic latex binders like those used in many paint formulations,
the most abundant VOCs include acetone and n-butanol. These
compounds, typically present at concentrations between 1 and
2500 ppm, do not affect performance properties like ease of application
and hiding power. They are added to facilitate various steps in the
paint's manufacture, or they are present as impurities. Their removal
would improve the nal paint formulation by removing the
unpleasant smell.
Ordinarily, the removal or stripping of trace amounts of low
molecular weight organics is easily accomplished by contacting
the liquid with air, nitrogen or steam. In a typical batch stripping
process, gas or vapor is blown through a sparger to create large
numbers of small bubbles. Sometimes the contacting is accomplished using a trayed or a packed tower. The organics transfer
from the paint to the gas phase due to favorable liquidvapor
equilibrium partition ratios or relative volatilities. Bubbles of gas
rise due to buoyancy, and quickly collect the volatile organics
because their large surface area overcomes the liquid's slow mass
n

Corresponding author. Tel.: 1 612 625 1596; fax: 1 612 626 7246.
E-mail address: cussler@umn.edu (E.L. Cussler).

0376-7388/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.memsci.2013.10.025

transfer. Because air or steam stripping is so effective, it is a widely

used separation process in environmental engineering, and is
supported by a large and vibrant literature [39].
However, air or steam stripping is difcult to carry out on latex
because it is stabilized by large amounts of surfactants. When the latex
is sparged with air or steam, the small bubbles desired for fast, efcient
removal of VOCs can produce large volumes of relatively stable foam.
This foam causes major problems in the processing and packaging of
the paint. Reducing the detergent concentration or changing the latex
properties may make air or steam stripping easier, but these alterations
are believed to compromise other properties of the paint.
In this paper we explore the use of membranes as an alternative means to remove VOCs from latex and to avoid foaming.
Such a process has been used in other situations [8,9]. In our
experiments, a nanoporous, hydrophobic membrane separates
owing latex paint from a stream of water-saturated air. The
membrane should stabilize the gaslatex interface, while potentially providing a large interfacial area for rapid VOC removal. The
membrane should also suppress bubble formation, and hence
eliminate foaming. At the same time, the membrane must not
signicantly retard mass transfer, because the desire to achieve
fast VOC removal motivates this work in the rst place.
In the following sections, we rst describe our experiments
with model solutions and with latex. We then report our results,
emphasizing the search for the mechanism of VOCs removal. This
mechanism is the key to judging if membrane-assisted stripping of
latex paint has commercial value.

2. Theory
To analyze the removal of organic compounds from this system,
we consider a reservoir of liquid containing one typical solute at

B. Ulrich et al. / Journal of Membrane Science 452 (2014) 426432

concentration c1. In our experiments, this liquid will either be an

aqueous solution of dissolved organics or an acrylic latex containing dissolved organics, that is, a surfactant-stabilized emulsion of
acrylic polymer and dissolved organics in water. This is the latex
binder used in formulating latex paint. The concentrations of
dissolved organics are dilute, well below their solubility in water.
The liquid is pumped at a volumetric ow L from the reservoir,
through a membrane module, and returned to the reservoir with a
changed solute concentration c1. The change in the reservoir
concentration c1 with time t is given by
V

dc1
Lc1  c1
dt

where V is the volume of solution in the reservoir. In our

experiments, V is nearly constant. We nd the concentration
c1 by writing a steady state mass balance for the concentration
change within the module. Because the liquid and gas in the
membrane module are nearly well mixed, their concentrations can
be approximated by single values. For the small module used here,
this is a good approximation; for cases where these concentrations
vary within the module, more complex analyses are available
elsewhere [10]. A mass balance over the entire module gives
p

L c1  c1 G 1  0
2
RT
where G is the volumetric ow of gas, and p1 is the solute's partial
pressure. A mass balance on the liquid alone yields
Lc1  c1 K L Ac1  cn1

where KL is the overall mass transfer coefcient based on a liquid

side driving force, A is the membrane area, and cn1 is the
hypothetical liquid concentration if the liquid were in equilibrium
with the gas. To dene cn1 we use the following:
cn1 kH p1

427

interface. The ux in the gas is given by

j1

kG
p  p1
RT 1i

10

where kG is the individual mass transfer coefcient in the gas and

p1i is the partial pressure of the solute in the gas at the gas
membrane interface. This much is the standard for many analyses
of mass transfer [1113].
The less familiar part is the analysis in the membrane itself.
Two types of membrane give different results. The rst type,
which is considered in this work, is a nanoporous hydrophobic
lm. In this case, the solute diffuses through the gas-lled pores.
The ux across the lm is
j1

DG
p  p1
lRT 1i

11

where DG is the diffusion coefcient in the gas, and are the

lm's porosity and tortuosity, respectively, and l is the lm's
thickness. On the other hand, the second type of membrane,
which is not studied in this paper, is a nonporous lm, which
may be either rubbery or glassy. In this case, solute dissolves in the
nonporous lm and diffuses within the polymer itself. The ux
across this type of lm is
j1

P
p  p1
lRT 1i

12

where P is the membrane permeability, the product of the solute's

solubility in the lm and its diffusion coefcient in the polymer lm.
We now can calculate the overall mass transfer coefcient KL as
a function of variables like kL, kG, and l. We do so by using Eq. (9)
(12) to eliminate the unknown interfacial concentrations. For the
nanoporous lm, the result is




1
j1 K L c1  cn1
c 1  k H p1
1=kL lkH RT=DG kH RT=kG
13

where kH is a type of Henry's law constant for the dissolved solute.

We now combine Eqs. (1)(4) to nd


dc1
1

c1
V
5
1=K L A 1= L kH RT=G
dt

For the non-porous lm, the result is





1
c1  kH p1
j1 K L  c10  cn1
1=kL lkH RT=P kH RT=kG
14

This is subject to the condition that the initial concentration is

known

Only Eq. (13) is tested experimentally in this paper.

The analysis, summarized by Eqs. (7) and (13), yields four
predictions which can be tested experimentally. First, a plot of the
logarithm of the concentration difference should be linear in time,
as suggested by Eq. (7). The second prediction is that the reciprocal
of the apparent rate constant 1/K should vary linearly with the
Henry's law constant kH , as suggested by combining Eqs. (8) and
(13) to get


1
1
A
l
1
A

kH RT

15
K
kL
L
kG
G
DG

t 0;

c1 c10

Integrating, we nd




c1
1
KAt
exp 
exp 
V1=K L A 1=L kH RT=G
V
c10

where K is an overall apparent rate constant

1
1
A
kH ART

K
KL
L
G

The apparent rate constant K reects a combination of three

different rate processes. If the liquid ow L and the mass transfer
product KLA are both large, then K is just a measure of gas ow G.
If the gas ow G and KLA are both large, then K is a measure of L.
If both L and G are large, then K represents only the overall mass
transfer coefcient KL.
The overall liquid mass transfer coefcient KL also has important characteristics. It results from three resistances in series:
those in the liquid, across the membrane, and in the gas. The ux
j1 out of the liquid is given by
j1 kL c1 

c1i

where kL is the individual mass transfer coefcient in the liquid

and c1i is the concentration in the liquid at the liquidmembrane

The intercept on this plot is a measure of both the mass transfer in

the liquid and of the liquid ow. We expect the slope on this plot
to include effects of the mass transfer through the membrane, of
mass transfer in the gas, and of the gas ow.
The third and fourth predictions deal with changes in K caused
by changes in the gas and liquid ows. Again, from Eqs. (7) and
(13) we expect
1
1
A lkH RT
kH RT kH ART

K
kL
L
DG
kG
G

16

The third prediction is that K varies with G. Because kG varies

non-linearly with G, this variation of K will be nonlinear. However,
if the mass transfer in the gas is fast, then the term containing
1=kG will be relatively small, and the reciprocal of K will vary with
the reciprocal of G. The fourth prediction is similar, but applies to

428

B. Ulrich et al. / Journal of Membrane Science 452 (2014) 426432

the variation of K with liquid ow L. From boundary layer theory

and from many empirical correlations, we expect the individual
coefcient in the liquid kL will vary with the square root of liquid
ow L. Thus the reciprocal of K should be linear with L  0:5 . We will
test all four of these predictions with the experiments described in
the following section.

Table 2
Elution Order and Retention Times of VOCs.
Isopropyl alcohol (from Fischer Scientic) was used
as an internal standard.

3. Experimental
3.1. Materials

Component

Retention time (min)

Methanol
Ethanol
Acetone
Isoproyl alcohol
t-Butanol
n-Butanol

3.3
5.2
6.5
7.1
0.2
11.4

An aqueous solution of VOCs was used to model the latex paint

for some experiments. Model solutions were prepared by weight
from distilled water and reagent grade organics. Methanol, ethanol, acetone, and t-butanol were from Sigma Aldrich, (St. Louis,
MO); ethyl acetate and n-butanol were from Fischer Scientic
(Pittsburgh, PA). Each VOC was present at 1000 ppm in the model
solutions.
A sample of acrylic latex was obtained from the Dow Chemical
Company (Midland, MI). The viscosity of the latex was between 20
and 50 cP at room temperature. The solids' concentration was
50.3%, and the mean particle diameter was between 0.122 and
0.125 m. The concentrations of VOCs in the latex are shown in
Table 1.
3.2. Analysis
VOC concentrations were measured using a Trace GC with
an FID. Helium was the carrier gas in an Agilent HP-1 capillary
column with a 5.0 m lm thickness. The sample loop was 2.0 mL
with a 1:10 split. The injector temperature was 150 1C and the FID
temperature was 250 1C. The oven temperature was rst held at
35 1C for 7 min, then ramped to 220 1C at 30 1C/min, and then held
at 220 1C for 1 min. The elution order and retention times are
listed in Table 2.
The response of the detector for the VOCs was calibrated for
concentrations from 10 ppm to 10,000 ppm. Calibration samples were
prepared by charging a 2.0 mL GC vial with 500 L of a standard
solution (containing all six VOCs to be analyzed in deionized water)
and 2.0 L isopropyl alcohol. The data in Fig. 1 show that the response
for each VOC is linear.
Concentrations of the VOCs in the aqueous model solution were
measured by 2.0 L liquid injections. Samples of model solution
were prepared by the same method as described for the calibration samples. Concentrations of VOCs in the latex samples were
measured by analyzing their headspace gas. A 1 g sample of latex
from the reservoir was placed in a 10 mL vial, and the vials were
Table 1
Concentrations of VOCs in Latex Sample. Similar VOCs were used in the model
solution. The Henry's law constants are at 25 1C.
VOCs in latex
sample

Conc.
(ppm wt)

Henry's law
constant
(M/atm)

Methanol
Ethanol
n-Butanol
Ethyl acetate
Acetone
t-Butanol
Benzaldehyde
Ethyl
propionate
Butyl acetate
Di-butyl ether
Butyl acrylate

127
123
4
25
2500
236
6
38

200
180
100
6.7
30

6.3
4.6

35
44
5

3.1
0.17
0.46

Fig. 1. GC-FID calibration data for VOCs in model solution. The response is linear
over a range of concentrations from 1 ppm to 10,000 ppm.

crimp-sealed with Teon-lined septa (Chromtech, Apple Valley,

MN). After the vials were left to cool and equilibrate at room
temperature overnight, 200 mL of the headspace gas was drawn
from the vials and injected into the GC.

3.3. Fouling
Several membranes were screened for their ux, fouling behavior
and solvent resistance. Flat membrane samples were placed in a
20 cm2 lter holder (Millipore Corp., Billerica, MA; Catalog no.
XX4404700) altered to have two inlets and two outlets. Dry, room
temperature nitrogen owed through the top compartment of the
cell and latex at 50 1C was cycled through the bottom compartment.
The total amount of water and organics was condensed in a cold trap
in a liquid nitrogen bath. The ux was determined by dividing the
mass of permeate collected by the time and membrane area.

3.4. VOC stripping

Stripping of both the model solution and the latex was measured
with the apparatus shown in Fig. 2. A at membrane was placed in
the altered Milipore lter holder. Water-saturated air at 50 1C was
cycled through the bottom compartment and latex or model
solution, also at 50 1C, was cycled through the top. The air was
saturated in a humidication column (24 in. tall, 1 in. diameter,
0.16 in. Ace Glass ProPac Packing). Heating tape kept the cell at
50 1C and aluminum foil wrapped around the cell reduced heat loss.
Experiments were typically conducted over 2 h, and samples were
collected from the reservoir every 2030 min. Samples of the model
solution were 0.5 mL and samples of the latex were 1.0 mL.
Apparent rate constants were calculated from Eq. (7).

B. Ulrich et al. / Journal of Membrane Science 452 (2014) 426432

429

Table 3
Membranes Tested for Fouling with a Dry Nitrogen Strip Gas. The most successful
membrane was the nanoporous polypropylene membrane.
Material

Fig. 2. VOC stripping apparatus. Measurements of the reservoir concentration

versus time were used to explore the mass transfer mechanism.

NF90
NF200
Nylon
Polypropylene (PP)
Cellulose acetate (CA)

Supplier

Dow
Dow
GE Osmonics
W. L. Gore
GE Osmonics

(m)

Overall ux
(g/cm2 h)

0.10
0.02
0.20

0.01
0.01
0.15
0.10

Pore size

4. Results
In this research we seek to remove the odor from latex binder used
in formulated latex paint by mass transfer across a membrane. The
odor, caused by low molecular weight organics, is difcult to remove
by conventional air stripping because the latex foams easily. However,
to be successful:
1. Membrane fouling must be minimal.
2. The rate of VOC removal must be fast compared to that for air
stripping.
3. The main resistances for mass transfer must be identied.
If we can measure these properties, we can make estimates of
the membrane areas needed to process commercial quantities
of latex.
4.1. Fouling
Membranes tested for fouling with dry nitrogen at 25 1C, as
well as the overall ux for each membrane, are reported in Table 3.
The cellulose acetate membrane crumbled because it was not
resistant to the latex, and the overall uxes from the Dow
membranes were approximately an order of magnitude lower
than the other membranes. The hydrophobic polypropylene and
hydrophilic nylon were chosen for further fouling studies.
The nylon membrane fouled signicantly, showing a 73%
decrease in ux after 20 h of continuous operation. The ux was
restored to 92% of the original value after washing with a cleaning
solution with base (sodium hydroxide) and detergent (sodium
dodecyl sulfate, SDS). It was not necessary to scrub or peel any
latex from the membrane. Thus, while the nylon membrane fouled
rapidly, it could be cleaned easily.
As Fig. 3 shows, the polypropylene membrane fouled much
more slowly than the nylon membrane, with a decrease in ux of
only 5% observed after 20 h of continuous operation. Though this
membrane was cleaned before it was shut down and left overnight, a lm deposited on the membrane, reducing the ux by 69%
in subsequent runs. After peeling the lm of latex from the
membrane, the ux was restored to 91% of the original value.
Film formation can be prevented by keeping both compartments
of the module moist when the system is shut down.
That the hydrophobic polypropylene membrane fouled more
slowly than the hydrophilic nylon membrane is the opposite of
many membrane experiments which ultralter biological macromolecules. There, hydrophobic membranes have more fouling and
the hydrophilic ones remain almost pristine [14]. Perhaps the
surfactant stabilizes the particles in the latex, causing less fouling
on the hydrophobic membrane.
We must stress that these results showing fouling are for VOC
and water removal with dry nitrogen. For experiments removing
VOCs with water-saturated air at 50 1C, no signicant fouling of
the polypropylene membrane was observed. While our data are

Fig. 3. Fouling of the polypropylene membrane. This membrane fouls more slowly,
but is more difcult to clean.

limited, we expect no major fouling with the hydrophilic membrane either if the stripping gas is saturated with water
or steam is used at the appropriate pressure to avoid excessive
temperatures.
4.2. Stripping of VOCs
We turn next to stripping experiments. The natural log of the
concentration of the reservoir ln c1 =c10 does change linearly with
time, as exemplied by the data in Fig. 4 for acetone both in the
model solution and in the latex paint. The slopes from plots like
this can be used to calculate apparent rate constants K.
The rate constant for acetone mass transfer from model
solution is 5.1 70.7  10  4 cm/s, 16% faster than transfer from
latex, which is 4.3 7 1.1  10  4 cm/s. However, since the error on
the rate constant is over 30%, there is little difference in the speeds
of mass transfer under the conditions chosen. The value for mass
transfer from the latex is a pleasant surprise. The latex is more
than 20 times more viscous than the model solutions, so we would
expect solution diffusion and hence mass transfer to be slower.
This is not the case, perhaps because the latex is somehow
facilitating solute transport.
4.3. Mechanisms
To understand the characteristics of VOC removal, we must
examine the mechanism for solute stripping in more detail. We
can do this by considering how the rate varies with the Henry's
Law constant kH , the liquid ow rate L, and the gas ow rate G.
Because in our experiments we vary kH more than L and G, its
variation is more instructive. Before we begin, we consider the
Henry's law constant of a latex in more detail, and in particular
how mass transfer is related to kH . The total amount of a volatile
solvent which can dissolve in an aqueous latex suspension
depends on the partitioning of the solute between the water and
the latex particles. Thus the total amount of a hydrophobic solute

430

B. Ulrich et al. / Journal of Membrane Science 452 (2014) 426432

for our experiments:

L
1:7 cm3 =s

0:085 cm=s
A
20 cm2

18

Thus the mass transfer resistance in the liquid is more signicant

than the resistance from the liquid ow rate, consistent with what
normally happens in gas stripping [1113]. Our estimate of the
intercept is
1
A
1
1
1100 s=cm

kL
L
10  3 cm=s 0:085 cm=s

Fig. 4. Acetone removal from model solution and from latex. In both experiments
the liquid ow L was 1.7 cm3/s and the gas ow G was 82 cm3/s. The rates are equal
within experimental error.

19

which is close to our experimental value of 1300 s=cm:

We next turn to the slope in Fig. 5, which is about 1 s/cm.
According to Eq. (15), this slope should contain the terms
1=kG l=DG A=G. The rst two terms represent the mass
transfer resistances in the water-saturated stripping gas and in the
gas-lled nanopores of the membrane, respectively. The third term
is the effect of the gas ow removing any evaporated organics
from the module.
As for our estimate for intercept, we can use the parameters of
our experiments to estimate these quantities. Neglecting for the
moment any correction for different solute volatilities, we can
estimate kG with the following equation [17]:
kG

DG
0:1 cm2 =s
1 cm=s

0:1 cm
lG

20

where DG and lG are the diffusion coefcient for a solute in the

water-saturated stripping gas and the thickness of the gas boundary layer, respectively. Because the membrane has 30% porosity, is
300 mm thick, and has pores with a tortuosity of about 3, the
resistance to mass transfer across the membrane is about
DG
0:1 cm2 =s 0:3
0:03 cm=s

0:3 cm 3
l

21

The third term is

Fig. 5. VOC stripping from model solution versus Henry's law constant. This plot is
consistent with Eq. (15).

can be much more in an aqueous latex than in water alone.

However, because the latex particles have a large surface area
per volume, we expect that they will quickly reach equilibrium
with water. Thus we will correlate our rates both in an aqueous
solution and in aqueous latex using the water-to-vapor Henry's
law constant. We thus avoid the more complex effective volatility
used in solubility studies [15,16].
After we measure K from plots like those in Fig. 4, we can plot
1/K vs. 1=kH as shown in Fig. 5. These results strongly support the
theory leading to Eq. (15). Moreover, the magnitude of the
intercept and the slope on this plot are consistent with our
estimates of the magnitudes of these quantities. More specically,
the intercept should equal [(1/kL) (A/L)], or the sum of the
resistances from mass transfer in the liquid phase and from the
liquid ow rate, respectively. The rst term will limit VOC removal
if the liquid diffusion coefcient is small, while the second term
will be limiting if the liquid ow rate is small. The slope reects
changes in volatility, both due to the membrane and to the mass
transfer in the gas phase.
We can make estimates of the resistances represented by the
intercept in Fig. 5. The liquid mass transfer coefcient kL can be
found from the lm theory of mass transfer:
kL

DL
10  5 cm2 =s
10  3 cm=s

0:01 cm
lL

17

where DL is the diffusion coefcient of a typical solute in the liquid,

approximately 10  5 cm2/s, and lL is the liquid boundary layer
thickness, typically 0.01 cm [17]. Next we calculate the value of L/A

G
20 cm3 =s

0:24 cm=s
A
82 cm3

22

Adding our results from Eqs. (20)(22) together we get our

estimate for the slope:
1
l
A
1
1
1

40 cm=s

kG
G
1 cm=s 0:03 cm=s 0:24 cm=s
DG
23
This rough estimate is the same order of magnitude as our
measured value of about 80 s/cm.
The success of Fig. 5 may seem surprising because the data on
which it is based include different VOCs which have different
diffusion coefcients in water and in gas. We should expect that
different solutes lead to different values of the mass transfer kL and
kG. Further study is needed to better understand the extent to
which differences in hydrophilic/hydrophobic character affect
mass transfer rates. For example, highly hydrophobic solutes are
likely to be strongly associated with latex polymer particles, and
may prove somewhat slower to strip from the latex compared to
highly hydrophilic solutes that tend to reside in the continuous
phase. Similarly, we could expect for the various solutions different partition coefcients and different boundary layer thicknesses
around latex particles. The fact that these apparently do not
occur afrms our use of a single airwater partition coefcient,
as discussed above.
Thus in our experiments, removal of VOCs from latex is largely
controlled by two resistances. The rst expected resistance is that
due to solute diffusion in the liquid, represented by 1/kL. The
second, unexpected one is mostly due to water-saturated gas in
the membrane's pores. To further evaluate the mass transfer
mechanism, we examine the effects of varied gas and liquid ow

B. Ulrich et al. / Journal of Membrane Science 452 (2014) 426432

431

Fig. 6. Mass transfer of acetone versus gas and liquid ow. The data are consistent with the expectation that 1/K varies linearly with G  1 and L  1/2.

rates on VOC removal. As discussed above, we expect plots of 1/K

versus G  1 and L  1/2 to be linear. To test this, stripping experiments were conducted with the model solution over a small range
of ow rates for the liquid (0.81.7 cm3/s) and the stripping gas
(80160 cm3/s). The results from these experiments, shown in
Fig. 6, are consistent with the dependence of these variations of K
with G and L. However, due to the limited accuracy of the data and
the relatively small ranges of G and L, this prediction is not proven.

5. Discussion
The results above lead to three important conclusions. First,
membrane-assisted stripping avoids latex foaming. This is simply
not a problem.
The second conclusion is that membrane fouling is minor if the
VOCs are stripped with water-saturated gas (or by extension, with
steam). This conclusion is more restricted than that on foaming,
because we have never continuously run our experiments for more
than a few days. To be successful commercially, we believe that any
membranes must be operated for about 3 years. Achieving this
length of service life may require periodic cleaning, an aspect which
we have not considered carefully. This point merits further study.
The third conclusion is that the mass transfer is about what is
observed in more conventional separation processes. In particular,
a nanoporous hydrophobic membrane offers little additional mass
transfer resistance. This conclusion is that expected from a wide
variety of experiments with many other membrane contactors,
including those suggested for gas absorption, liquidliquid extraction, and differential distillation [1822]. It is important to have
this afrmed experimentally for stripping of VOCs from latex,
which is what is done in this paper.
However, this positive conclusion should be tempered by
other experience using microporous polypropylene membranes.
While these membranes often give successful rates for the rst
few days, the membrane's pores can then wet and the membrane's mass transfer rates can decrease. These slower rates often
involve solvents or detergents which facilitate pore wetting. We
saw no evidence of these effects here, but we did not look at the
longer operating times where they would be expected to occur.
If these slower rates do occur, they can sometimes be managed
by lling the pores with a hydro-gel like polyvinylalcohol.
We can use the experimental results to estimate the membrane
area required for latex processing. To make this more specic,
imagine that we wish to remove 90% of the VOC content from ten
tonnes of latex per day, or a ow of 120 cm3 latex/s. We can
imagine carrying out this stripping either across a membrane
connected to a stirred tank or in a hollow ber membrane module.
For the stirred tank, the membrane would be at sheets, which
give a small membrane area per latex volume but can be easily

disassembled for cleaning. From a balance on the VOCs in the

stirred tank, we obtain
c1
1

1 KA=L
c10

24

c1
1=5  10  4 cm=sA
0:1
c10
120 cm3 =s

25

A 200 m2

26

where c1/c10 is the fraction of VOC content remaining, and K is the

overall rate constant determined in this work. For a hollow ber
module, the area needed is smaller [16]. A mass balance on the
VOCs in bers surrounded by a high gas ow gives
c1
e  K L A=Q
c10
4
c1
0:1 e  f1010
c10

A 30 m2

27
cm=sA=120 cm3 =sg

28
29

where c1/c10 is again the fraction of VOC content remaining and KL

is the overall mass transfer coefcient inferred at high gas ow from
this work. This assumes that the latex is owing within the hollow
bers. Other studies of different module designs suggest that KL can
be increased by about ve times by having the latex ow outside of
and across a bed of hollow bers [23]. This suggests a strategy for
decreasing the membrane area still more, though the hollow bers
will be much more difcult to clean than at membranes. On this
basis we believe this membrane-assisted removal of trace VOCs
from latex used for paint has considerable potential.
Acknowledgments
The authors are indebted to W.A. Arnold, M.L. Trippeer, and
Grant A. Von Wald for helpful discussions, and to Andrew Wagner
for help with preliminary experiments. This work was supported
by the Dow Chemical Company.

Nomenclature
A
c1
c01

membrane area
volatile solute concentration in reservoir, moles
per volume
volatile solute concentration in module, moles
per volume

432

cn1
DG ; DL
G
kG
kH
kL
K
KL
L
l
P
p1
R
T
t
V

B. Ulrich et al. / Journal of Membrane Science 452 (2014) 426432

hypothetical volatile solute concentration in liquid

in equilibrium with gas
diffusion coefcients in gas and liquid respectively
gas ow, volume per time
individual gas mass transfer coefcient, length
per time
a Henry's law coefcient, moles per volume per
pressure
individual liquid mass transfer coefcient, length
per time
apparent rate constant, length per time
overall mass transfer coefcient, length per time
liquid ow, volume per time
membrane thickness
permeability
partial pressure of volatile solute
gas constant
temperature
time
reservoir volume
void fraction in membrane
tortuosity in membrane

References
[1] D. Stoye, B. Marwald, W. Plehn, Paints and coatings. 1. Introduction, Ullmann's
Encyclopedia of Industrial Chemistry, Wiley, 2010.
[2] P. Wolkoff, How to measure and evaluate volatile organic compound emissions from building products. A perspective, Sci. Total Environ. 227 (1999)
197213.
[3] J.L. Fleming, Volatilization Technologies for Removing Organics from Water,
Noyen data, Park Ridge, NJ, 1990.
[4] Y.L. Hwang, G.E. Keller, J.D. Olson, Steam stripping for removal of organic
pollutants from water. 1. Stripping effectiveness and stripper design, Ind. Eng.
Chem. Res. 31 (1992) 17531759.
[5] Y.L. Hwang, J.D. Olson, G.E. Keller, Steam stripping for removal of organic
pollutants from water. 2. Vapor liquid equilibrium data, Ind. Eng. Chem. Res. 31
(1992) 17601768.

[6] R.E. Hinchee, Air Sparging for Site Remediation, CRC Press, Boca Raton,
FL, 1994.
[7] J.R. Ortiz-Del Castillo, G. Guerrero-Medina, J. Lopez-Toledo, J.A. Rocha, Design
of steam-stripping columns for removal of volatile organic compounds from
water using random and structured packings, Ind. Eng. Chem. Res. 39 (2000)
731739.
[8] J.G. Crespo, K.W. Boddeker, Membrane Processes in Separation and Purication, Springer Verlag, Berlin, 2010.
[9] I. Abou-Nemeh, S. Majumdar, A. Saraf, K.K. Sirkar, L.M. Vane, F.R. Alvarez,
L. Hitchens, Demonstration of a pilot-scale pervaporation systems for volatile
organic compound removal from a surfactant enhanced aquifer remediation
uid, Environ. Prog. 20 (2001) 6473.
[10] L. Dahuron, E.L. Cussler, Protein extractions with hollow bres, AIChE J. 34
(1968) 130136.
[11] C.J. Geankoplis, Transport Processes and Separation Process Principles, 3rd ed.,
Prentice Hall, Upper Saddle River, NJ, 2003.
[12] W. McCabe, J.C. Smith, P. Harriot, Unit Operations of Chemical Engienering, 7th
ed., McGraw-Hill, New York, NY, 2005.
[13] J.D. Seader, E.J. Henley, Separation Process Principles, 3rd ed., Wiley, Hoboken,
NJ, 2010.
[14] M.A. Shannon, P.W. Bohn, M. Elimelech, J.G. Georgiadis, J.B. Marinas,
A.M. Mayes, Science and Technology for water purication in the coming
decades, Nature 452 (2008) 301310.
[15] T.C.G. Kibbey, K.D. Pennell, K.F. Hayes, Application of sieve-tray air strippers to
the treatment of surfaction-containing wastewaters, AIChE J. 47 (2001)
14611470.
[16] C. Zhang, G. Zheng, C.M. Nichols, Micellar partitioning and its effects on
Henry's law constants of chlorinated solvents in anionic and nonionic
surfactant solutions, Environ. Sci. Technol. 40 (2006) 20214.
[17] E.L. Cussler, Diffusion, 3rd ed., Cambridge University Press, New York, NY,
2009.
[18] Q. Zhang, E.L. Cussler, Microporous hollow bers for gas absorpion, J. Membr.
Sci. 23 (1985) 321345.
[19] R. Prasad, K.K. Sirkar, Dispersion-free solvent extraction with microporous
hollow bers modules, AIChE J. 34 (1988) 177188.
[20] D. Yang, R.S. Barbero, D.J. Delvin, E.L. Cussler, C.W. Colling, M.E. Carrera,
Hollow bers as structured packing for olen/parafn separation, J. Membr.
Sci. 279 (2006) 6169.
[21] D. Yang, J.D. Devlin, R.S. Barbero, R. Wright, E.L. Cussler, Hollow bers as
structured packing for olen/parafn distillation, in: Proceedings of the World
Congress of Chemical Engineering, Montreal, Canada, August 2009.
[22] E. Bringas, M.F. San Roman, J.A. Irabien, I. Ortiz, Overview of the mathematical
modeling of liquid membrane separation processes in hollow ber contactors,
J. Chem. Technol. Biotechnol. 4 (2009) 1531614.
[23] S.R. Wickramasinghe, J.J. Semmens, E.L. Cussler, Mass transfer in various
hollow ber geometries, J. Membr. Sci. 69 (1992) 235250.