Académique Documents
Professionnel Documents
Culture Documents
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
2. Theory
To analyze the removal of organic compounds from this system,
we consider a reservoir of liquid containing one typical solute at
dc1
Lc1 c1
dt
427
kG
p p1
RT 1i
10
DG
p p1
lRT 1i
11
P
p p1
lRT 1i
12
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
K
KL
L
G
c1i
K
kL
L
DG
kG
G
16
428
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
Methanol
Ethanol
Acetone
Isoproyl alcohol
t-Butanol
n-Butanol
3.3
5.2
6.5
7.1
0.2
11.4
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.
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.
429
Table 3
Membranes Tested for Fouling with a Dry Nitrogen Strip Gas. The most successful
membrane was the nanoporous polypropylene membrane.
Material
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
0:085 cm=s
A
20 cm2
18
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
DG
0:1 cm2 =s
1 cm=s
0:1 cm
lG
20
0:3 cm 3
l
21
DL
10 5 cm2 =s
10 3 cm=s
0:01 cm
lL
17
G
20 cm3 =s
0:24 cm=s
A
82 cm3
22
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
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.
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
1 KA=L
c10
24
c1
1=5 10 4 cm=sA
0:1
c10
120 cm3 =s
25
A 200 m2
26
A 30 m2
27
cm=sA=120 cm3 =sg
28
29
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
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.