MOST PROMISING TECHNIQUES FOR VOCs REMOVAL IN LATEX (EMULSION)

PAINTS – A Review
Jigesh P. Mehta1,Dharmesh V. KaPatel2
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Department of Chemical Engineering, G H Patel College of Engineering & Technology, Gujarat Technological University,
Vallabh Vidyanagar, Anand–388120, Gujarat, India.
[email protected], [email protected]
Abstract: Air pollution is the presence of any substance in the atmosphere at a concentration high enough to produce an
undesirable effect on humans, animals, vegetation or materials, or to significantly alter the natural balance of any eco-system.
VOCs (volatile organic compounds) are also a type of pollutant in the air; they causing nausea, irritation and some are also
toxics which are detrimental to humans and environment. There is a significant need of fully satisfactory method for removal of
VOCs. There are several methods including physical as well as chemical treatments available to remove VOCs. The present
study describes theoretical summary of the available methods for VOCs removal in latex (Emulsion) paint and describes one of
the prominent technique of VOCs removal by devolatilization using vacuum system. The important factor in the devolatilization
is molecular diffusion of free monomers due to concentration gradient. This review includes effect of temperature, pressure,
correct choice of adsorbent and area of mass transfer on devolatilization of emulsion (latex paint) containing different
monomers. Based on theoretical calculation, it has been proved that devolatilization is also a promising technique for the
removal of VOCs.
Keywords: - VOCs, devolatilization, molecular diffusion, latex paint.

1. Introduction
Paint is one of the oldest synthetic substances known from history stretching back long ago and Emulsion (latex paints) are
water-borne paints, in which the resin binders are dispersed in the solvent in form of small insoluble resin particles (colloids and
coarse dispersions). Emulsion paints contain 50-60% of solids dispersed in the water-based dispersion media consisting of water
and up to 5% of water miscible organic Solvents (alcohols, glycol ethers). Solvent is added to water in order to promote the
coalescence of the dispersed binder particles during the paint drying. Emulsion paints provide permeable (“breathing”) coatings
with lower disposition to peeling and are characterized by moderate corrosion protection and low gloss.
Latex paint has an odor which when a Layman enters into a newly and freshly painted room, he will not only notice the color
and smoothness of the painted surfaces, but also the smell. Most of the Human beings are having the nature of not liking this
type of smell as it causes headache and irritation to the one who remains in frequent contact. The simplest way of reducing this
smell from the room is flushing it from the ventilator once in a day or so but it is not the proper solution to it and Thus VOCs
have become a major challenge for the Paint industry which needs to be taken into consideration. Volatile Organic Compounds
(VOCs) are man-made and/or naturally occurring highly reactive hydrocarbons. VOCs can be any organic compound whose
boiling point is in the range from (50-100°C) to (240-260°C). Many types of VOCs are toxic or even deadly to humans and can
be detrimental to the environment. A majority of VOCs are created from anthropogenic activities consisting of manufacturing
industries, petrochemical industries and vehicular emissions. So, the ultimate objective here is to investigate the various physical
and chemicals methods available and try to differentiate between them the best way of removing the VOCs. Devolatilization is
one the appropriate way of removing the VOCs from Emulsion paints.
2. Physical Methods:-
2.1. VOCs adsorption by using adsorbent:
Adsorption is the trapping of monomers who are free or unreacted on a surface area material. The unreacted monomer gets
adsorbed onto the adsorbent material such as activated carbon physically.
2.1.1 Activated carbon based adsorption: [1,2,3]
Carbon adsorption is a very common method of VOCs emission control. VOCs are removed by physical adsorption. Carbon
adsorption systems are flexible and inexpensive to operate and Installation costs are often lower than those of other systems. The
adsorption capacity of activated carbon for a given VOC is represented by an adsorption isotherm of the amount of VOC
adsorbed (adsorbate) to the equilibrium pressure (concentration) at constant temperature. VOC molecules are physically
attracted and held to the surface of the carbon.
Activated carbon is such a good adsorbent because of its large surface area, which is a result of its vast infrastructure of pores
and micro-pores. In a commercial activated-carbon solvent-recovery plant, VOCs emulsion passes through a tank containing a
bed of activated carbon. The solvent is adsorbed on the carbon surface and VOC free emulsion is obtained. When all of the
available surfaces of the carbon pores are occupied, it will not adsorb any additional solvent and to recover the solvent for reuse,
it must be released from the carbon surface. This is most commonly done by heating the carbon with steam. The hotter the
carbon, the less solvent it can hold, so as the steam heats the carbon, solvent is released and flushed away by the steam. By the
help of simple gravity decanting, the mixture of steam and solvent is condensed by cooling and separated. If the solvent is
soluble in water, decanting is replaced by Distillation.

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The batch process of adsorption and desorption can be made continuous by the use of multiple carbon beds so that one can be
off-line for desorption while the other is on-line for adsorption. Activated carbon is found to be the correct choice for high
capacity adsorption of monomers, most VOCs with molecular weights between 40 and 150 and boiling points from 100°F to
500°F.
Many parameters need to be studied in detail before deciding about the adsorption process to be performed or not like
description of the process emitting the VOCs, temperature, pressure, composition of the VOCs and their concentrations, any
contaminants present and so on. [2, 3] Besides this there are other adsorbent which are also being used for the removal processes
such as zeolite, fly-ash, silica-gel.
2.2 Membrane-assisted VOC removal from aqueous latex: [4,5]
Volatile organic compounds (VOCs) in aqueous mode and latex binder used for formulating latex paint can be stripped without
foaming by using a micro porous hydrophobic polypropylene membrane. The membrane assisted method is characterized by
imposition of a barrier (membrane) generally made of polymeric material. The characteristic of the membrane selected for a
particular application are dependent on the organic compound to be separated. However membrane efficiency requires large
contact surface area.
The latex is passed through a hollow fiber while dried stripping air is passed counter or concurrently through the exterior of the
fibers. Mass transfers of the free-radical which is to be removed occur across membrane barrier from the lumen side to the shell
side. In packed tower air stripping mass transfer of VOCs from the liquid phase to the air phase takes places through intimate
direct contact between the two phases, while mass transfer in hollow fiber occur at the interface of the air filled membrane pores
and the liquid filled fiber lumen. The concentration gradient between two has acts as the driving force for this transfer.
The concentration gradient is maintained by instantly sweeping away the VOCs crossing the barrier into the stripping air,
thereby, maintain an essential near zero VOC concentration on the shell side.
2.3 Stripping Technique for VOCs removal: [6,7,8,9]
Stripping is commonly employed industrially to remove residual monomer of the polymer product, especially of those in the
form of latexes. In this technique, steam or gas is passed through the resin and monomer is carried out.

Figure:1
Ordinarily, the stripping of trace amount is in such a way that the flow molecular weight organics is easily accomplished by
contacting the liquid with air, nitrogen or steam. In a typical batch stripping process, gas or vaporize blown through a Spurger to
create large numbers of small bubbles. Sometimes the contacting is accomplished using a tray or a packed tower. The organics
transfer from the paint to the gas phase due to favourable liquid–vapor equilibrium partition ratio. Bubbles of gas Rise due to
buoyancy, and quickly collect the volatile organics because their large surface area over comes the liquid's slow mass transfer.
Because air or steam stripping is so effective, it is a widely used separation process in environmental engineering, and is
supported by large and vibrant industries.
Several different types of stripping apparatus have been available now a day. Those apparatus include: batch, semi-batch and
continuous tank strippers, single stage vacuum strippers, continuous stripping with cross-flow gas or counter-current gas flow,
continuous counter-current stripping columns, etc.
Because of the small particle sizes obtained in emulsion polymerizations, steam and/or gas stripping procedures have
successfully reduced the residual monomer. Reduction of the residual monomer to a level of a few ppm is in general not
possible with steam stripping in equipment with a realistic size. The time constants for monomer transport in the polymer phase
are very high.
2.4 Removal of VOCs by Supercritical fluid Extraction: [10,6,11]
Recently, the usage of supercritical fluids to extract impurities from polymers has received a special attention. Supercritical de
volatilization has the potential to produce high-purity, high-quality products with lower energy costs. Successful commercial
technologies for processing polymers by using the supercritical fluids are still limited, but, in order to meet the stringent
requirements in an economical way, this alternative is being considered more seriously nowadays.

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Emulsion polymerization is a free radical polymerization in a heterogeneous reaction system, yielding a colloidal stable
dispersion of. Due to diffusion limitations in the particle phase the polymerization reaction will not proceed to completion. As a
consequence, the polymer latex product contains a significant amount of residual monomer inside the polymer particles,
generally in the range of a thousand parts per million (ppm). Reduction of the residual monomer level in polymer latex products
is essential for safe and non-toxic use. Moreover, increasingly stringent requirements demand for further reduction of residual
monomer in polymer products. Various conventional techniques to reduce the residual monomer level in polymer latex products
are energy intensive, time consuming. Most important, conventional techniques are not able to fulfill the basic requirements as
the result of thermodynamic and transport limitations. Consequently, monomer partitioning between the polymer phase and the
vapor phase is characterized by very low monomer partial pressures in the vapor phase. Reduction of the residual monomer to a
level of a few ppm is in general not possible with steam stripping in equipment with a realistic size.
An alternative technique to reduce the residual monomer amount in polymer latex systems is the extraction with high pressure
carbon dioxide (CO2). For example, at high pressures a SCF has solubility and density properties close to those of a liquid, but
with considerable larger diffusion coefficients and lower viscosity. The most important advantage of using high pressure CO2 is
that CO2 increases the fugacity of the monomer in the polymer phase, thereby increasing the monomer molar fraction in the gas
or SCF phase, as a result of swelling the polymer is softened and plasticized. Monomer transport rates in the polymer phase
swollen with CO2 increase from lower values to higher valves leading to improved monomer transport rates.
In a typical supercritical de volatilization process the first step is the compression of the fluid to elevated pressures above its
critical pressure. The second stage is the extraction stage, in which polymer is exposed to supercritical fluid, it is swollen, the
key volume in the polymer is increased, and, consequently, the diffusion of the impurities out of the polymer is enhanced. The
final stage in supercritical de volatilization is the depressurization stage when pressure is reduced and supercritical fluid diffuses
out of the polymer.
Compared with liquid solvents, supercritical fluids possess greater ability to diffuse as well as lower density and viscosity.
Therefore, supercritical fluids can be products of choice for carrying out selective extractions.
3. CHEMICAL METHOD:
Some specific compounds are used for reducing residual monomer content, as they react with the monomer‟s double bond
converting residues into safe derivatives and that are preferably more easily removed by a further devolatilization procedure.
3.1 Method of reducing the residual monomer content of a paint emulsion by ozone: [12,13,14]
The method involves contacting an aqueous dispersion of a saturated polymer with ozone under conditions whereby the ozone
reacts with the unsaturation of the monomer in the dispersion. The invention can be practiced using generally any conventional
apparatus suitable for contacting an aqueous dispersion of saturated polymer with a gas stream containing ozone in an amount
sufficient to achieve the desired reduction of residual monomer by an ozonolysis reaction. The method can be carried out in a
batch, semi-batch, or continuous mode using conventional stripping equipment such as wetted wall towers, packed towers or
spray towers, or more preferably by bubbling (sparging) a gas containing ozone through a vessel containing the aqueous
dispersion. Continuous stirred reactors wherein gas containing ozone is bubbled into the dispersion at the bottom of the reactors
are also suitable.
The ozone used in the method may be generated by passing air or oxygen through a commercial ozone unit wherein ozone is
produced by an electrical arc or spark generated in the presence of the air or oxygen.
Pressure and temperature conditions for the ozonolysis reaction may vary. The pressure in the reactor or apparatus wherein the
dispersion is contacted with the gas containing the ozone is not believed to be a reaction rate controlling variable. Ozone is a
strong oxidizing agent and reacts readily with the unsaturated monomers at moderate or even low temperatures. Accordingly, it
is generally unnecessary to heat the contents of the reactor or apparatus wherein the ozonolysis is being carried out. Suitable
temperatures for the ozonolysis reaction vessel can generally range from about 10˚C, 15˚C in the range from about 25˚C
preferred.
The time needed for the ozonolysis reaction may vary depending on the initial concentration of the unsaturated monomer, the
chemical reactivity of the unsaturated monomer, desired level of reduction of the unsaturated monomer, concentration of ozone,
and temperature. Generally speaking, the reaction time may range from as little as seconds to as long as hours. The method of
the invention can be used by itself, but is more preferably used as a final step in reduction of residual unsaturated monomer
content, such as in conjunction with conventional steam and/or inert gas stripping. In this preferred mode, the majority of
residual unsaturated monomer in the aqueous polymer dispersion is physically removed from the aqueous dispersion using
steam and/or inert gas stripping to facilitate recovery and recycling of most of the residual monomer, thereby reducing the
amount of ozone needed to chemically react with the unsaturated monomer. Accordingly, the method can be used with
conventional manufacturing facilities which have been augmented to accomplish the ozonolysis reaction accordingly.
3.2 Reduction of VOCs by Re-active co-monomers: [13]
There are several issue with this samples that we have to first look for such scavenger monomers which will not only react with
free monomers but also will remain inactive with other composition of paints. Besides this we have this scavenger monomers
are likely to have more attraction with one specific VOCs into the sample so to we have to add no of such monomers to get read
of VOCs and then it may be possible that it can further aggravate this process. [5,11]

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4. Devolatilization of Emulsion paint under vacuum:-
In this process the paint sample is submitted to sub-atmospheric pressure and at particular temperature in such a way that
monomer is volatilized reducing the residual monomer content. The driving force for the diffusion of volatile compound from
the emulsion is the concentration gradient.
4.1 Diffusion: [15, 16, 17]
Diffusion describes the spread of particles through random motion from regions of higher concentration to regions of lower
concentration. The higher the diffusivity (of one substance with respect to another), the faster they diffuse into each other.
Diffusion is the basic mass transfer mechanism in numerous industrial operational. It occurs in all mass transfer operation.
Diffusion rate determine mass fluxes, are related to process efficiencies and thus are basic to design operation of process
equipment.
4.1.1 Molecular diffusion:
Diffusion produced by a concentration gradient is the most common mass transfer process. A concentration gradient moves the
component of mixture in the direction of the gradient to equalize concentration. Steady state diffusion requires the component
and removal of the diffusion component.
4.1.2 Fick’s Law:
The rate of diffusion is governed by Fick‟s law. This states that the rate of diffusion is proportional to the concentration gradient
and to ease with which the molecules will move. The latter property is called the Diffusivity.
4.1.3 Calculation for Diffusivity:
The diffusivity or diffusion coefficient, D AB is a property of the system dependent upon temperature, pressure, and nature of the
components.
If the experimental data for DAB is known then we can calculate for the required D AB by the help of Wilke-lee equation:-
D𝐴,B1/D𝐴,𝐵2 = (T1)3/2 * P2 /(T2)3/2 * P1
4.1.4 Mass transfer coefficient:
In engineering, the mass transfer coefficient is a diffusion rate constant that relates the mass transfer rate, mass transfer area, and
concentration change as driving force.
5. Suggested operating conditions for the experiment:-
In the experiment, one need to remove VOCs from emulsion paint. These VOCs are nothing but free monomers present in
samples. In the method of de-volatilization under vacuum temperature, pressure, area of mass transfer are the parameters which
need to be kept in mind:

Table 1: Operating parameters for design of experiment

Parameters Operating range

System temperature 40˚c-60˚c

System pressure 200mmHg
Area of mass transfer 20cm2-100cm2

5.1 Factors affecting the Process:-

5.1.1 System Temperature:
A substance with a high vapor pressure at normal temperatures is often referred to as volatile. The atmospheric pressure boiling
point of a liquid (also known as the normal boiling point) is the temperature at which the vapor pressure equals the ambient
atmospheric pressure. With any incremental increase in that temperature, the vapor pressure becomes sufficient to overcome
atmospheric pressure and lift the liquid to form vapor bubbles inside the bulk of the substance.
Therefore temperature is a vital parameter of the processes, in the present method the system temperature is kept at 40˚c and
50˚c. Though VOCs are so much volatile that it start releasing at room temperature but this process are comparatively very slow.
Even the temperature of a system is desired to be kept below 80˚c because paint are generally emulsion so increasing the
temperature may affect its property.
5.1.2 System Pressure:
The system is kept under vacuum, because in vacuum we can achieve desired results at lower temperature and also the driving
force in processes is vapor pressure. In this process the system pressure are kept in between 20kpa to 25kpa.system pressure
depends upon the vapor pressure of the composition so as samples have different composition of VOCs so correspondingly the
system pressure must be kept above their vapor pressure. If the pressure is kept below vapor pressure then there is possibility
that those VOCs may remain in to the sample. Besides this as the system is under vacuum so we need to take care that there
should not be any leakage or else it would have adverse effect on our system.
5.1.3 Area of Mass Transfer:

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Mass transfer directly depends upon the available surface area. Larger the area more will be the rate of diffusion. In are
experiments we are trying to create a new surface every time by stirrer, so the rate of mass transfer will be faster.
5.1.4 Choice of Adsorbent:
Adsorbent also play important role in trapping the removed volatile compound which released from the sample. So the
adsorbent which is selected should have larger pore size as well as it should not degrade at higher temperature besides it should
be more affinitive towards organic compound. There various adsorbent which are been used for this purpose such as activated
carbon, zeolite, silica gel and so-on.
Activated carbon (granular) is been used as adsorbent because firstly it has very large pore size, secondly it is good in handling
organic compound. Even the availability is goods. Granular form of carbon is been used because it will work as a packing and,
even it is easy to handle because as the system is under vacuum so there is a possibility that under succession those small
particles will travel into the vacuum pump an may cause trouble.
6. Conclusion:-
VOCs have become a major challenge for the Paint industry which needs to be tackled. By reviewing literature available on
conventional technique for VOCs removal like stripping, by using adsorbent or by treating it with supercritical fluid, even b y
help of chemical treatment. It is been concluded that the result obtain by them are effective but there are certain problem arises
while implementing them at large scale.
Based on theoretical calculation and investigation, it is found that devolatilization is most promising technique for the removal
of VOCs. The literature results that as the system temperature increases from 40˚c to 60˚c, there is an increase in percentage
removal of monomers of about 60 to 80% for each monomers. There is also a similar trend is observed for removal of
monomers with time from 20 to 40 min. Further increase in percentage removal would be reported by increasing the system
temperature and time.
The final analysis justifies that the method is potential for removing the significant amount of monomers from the system.
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