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Chemical Engineering Science 57 (2002) 3929 – 3937

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Process design for the removal of residual monomer from latex products
using supercritical carbon dioxide
Maartje Kemmere∗ , Mascha Cleven, Marcus van Schilt, Jos Keurentjes
Department of Chemical Engineering and Chemistry, Process Development Group, Dutch Polymer Institute, Eindhoven University of Technology,
P.O. Box 513, 5600 MB Eindhoven, The Netherlands
Received 4 October 2001; received in revised form 14 May 2002; accepted 11 June 2002

Abstract

One of the most important environmental incentives for the polymer industry is to reduce the residual monomer in polymer products.
Although several techniques are available for the removal of residual monomer, most methods are rather energy intensive and time
consuming. Since supercritical carbon dioxide (scCO2 ) is known to have a plasticizing e4ect on many polymers and is a good solvent
for most commonly used monomers, a scCO2 -based process forms an interesting alternative. This paper focuses on the development of
a post-emulsion polymerization process, which decreases the amount of methylmethacrylate (MMA) in polyMMA lattices using scCO2 .
Typically, the method comprises a counter7ow process, in which part of the residual monomer is converted by the increased di4usion inside
the polymer particles due to the swelling by scCO2 . In addition, the amount of residual monomer is further reduced by the extraction capac-
ity of scCO2 . Experimental studies have shown that the scCO2 extraction of MMA is the predominant e4ect as compared to the enhanced
polymerization due to plasticization. From a mass transfer model, the largest resistance in the extraction process appears to be situated in
the water phase near the scCO2 interface due to a relatively small surface area as compared to the overall polymer–water interfacial area. A
viability study, including equipment sizing and economic evaluation, has shown that the removal of residual monomer from latex products
using scCO2 in principle yields a process which is both technically and economically feasible, capable to meet the future requirements.
? 2002 Elsevier Science Ltd. All rights reserved.

Keywords: Residual monomer; Supercritical carbon dioxide; Emulsion polymerization; Extraction; Process design; Partitioning coe;cient

1. Introduction major disadvantage of this kind of operation is the di;-


culty to reach complete monomer conversion at processing
Emulsion polymerization is a free radical polymeriza- temperatures typically below the glass transition temper-
tion performed in a heterogeneous reaction system, yielding ature (Tg ) of the polymer. This phenomenon is primarily
submicron solid polymer particles dispersed in an aqueous explained by the fact that the di4usion coe;cients in the
medium, called a latex. Since the beginning of the poly- polymer particles critically depend upon the weight frac-
mer industry in the 1940s emulsion polymerization pro- tion of polymer. As a consequence, the di4usion-controlled
cesses have become important for the production of synthetic propagation rate coe;cient decreases at a higher conver-
rubbers, paints, coatings and adhesives. Currently, approxi- sion (Maxwell, Verdurmen, & German, 1992). Therefore,
mately 15% of the annual polymer production in the Western at polymerization temperatures below the Tg and at high
world are produced using an emulsion polymerization pro- conversion the reaction rate ultimately vanishes before
cess (Gilbert, 1995). In general, emulsion polymerization monomer conversion is complete. These di;culties often
achieves relatively high reaction rates. However, large-scale result in the presence of substantial amounts of residual
industrial emulsion polymerizations are preferably operated monomer in the Fnal product of the emulsion polymerization.
at relatively low temperatures in order to control the rate
of heat production and to prevent thermal runaway, as the 2. Various techniques for the removal of residual
usual high solids polymerization processes can su4er from monomer
considerable heat transport limitations (Poehlein, 1997). A
For health, safety and environmental reasons, signiFcant
∗ Corresponding author. Tel.: +31-40-2473673; fax: +31-40-2446104. e4orts have been made to reduce the residual monomer
E-mail address: m.f.kemmere@tue.nl (M. Kemmere). content in commercial lattices. Some techniques for

0009-2509/02/$ - see front matter ? 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 0 2 ) 0 0 3 3 9 - 1
3930 M. Kemmere et al. / Chemical Engineering Science 57 (2002) 3929 – 3937

residual monomer removal are already applied industrially, The limiting factor for mass transfer is shown not to be in the
others are still being investigated. In general, the available polymer particles, mainly because of the high speciFc area
methods are based on two concepts, i.e. conversion or ex- of the polymer–water interface as compared to the mem-
traction of the residual monomer. Slow di4usion-controlled brane area. Although the high initial costs as well as foul-
propagation can be overcome by increasing the tempera- ing of the membrane surface with the polymer particles are
ture, thus lowering the particle viscosity and enhancing the potential drawbacks, pervaporation may thus be expected
di4usivity of the monomer. Starting the polymerization at to provide a viable alternative. Table 1 summarizes the ex-
a relatively low temperature ensures a controlled conver- isting techniques for the removal of residual monomer. At
sion of the larger part of the monomer. Subsequently, the present the industrial practice of emulsion polymerization
reaction rate decreases and the temperature can be safely mainly involves thermally enhanced di4usion and a combi-
increased to complete the conversion of monomer (Mayer, nation of steam and chemical stripping. As mentioned above,
Meuldijk, & Thoenes, 1995). Although this technique is all these techniques come with their speciFc disadvantages.
relatively simple and no additional chemicals are required, Since legislation on levels of residual monomer in consumer
the need for an additional large post-reaction tank and the products is expected to become more severe in the near fu-
high-energy consumption hampers the economic viability ture, there is considerable room for improvement of the ex-
of this technique, especially when future regulations on isting techniques.
residual monomer become more severe. In addition to ther- Supercritical CO2 (scCO2 ) potentially forms an interest-
mally enhanced monomer di4usion, swelling the polymer ing alternative for residual monomer removal as it com-
particles with an inert diluent, thus reducing the weight bines both approaches mentioned earlier, i.e. simultaneous
fraction of polymer, has been shown to increase monomer conversion and extraction of the monomer. First of all,
di4usivity as well (Chen & Lee, 1992). Due to a plasti- the plasticizing e4ect is expected to enhance di4usivity in
cizing e4ect mass transport within the polymer particle is the polymer particles, as they swell in scCO2 (Kendall,
signiFcantly enhanced. Consequently, the di4usion- Canelas, Young, & DeSimone, 1999). This would increase
controlled propagation rate does not decrease as it gener- the di4usion-controlled propagation rate of the polymeriza-
ally does at high conversions. However, this implies the tion and thus further complete the conversion of monomer
introduction of an extra component that later has to be re- within an acceptable time of operation. Secondly, the en-
moved from the Fnal product. This technique thus requires hanced di4usivity within the polymer particles is expected
an additional post-processing step. Biological degradation to facilitate the transport of monomer through the polymer
by means of adding a peroxide-generating enzyme has been particles to the aqueous phase. Moreover, scCO2 is an ex-
shown to reduce the amount of monomer in a latex, as the cellent extraction medium for a variety of monomers as little
latter reacts with the radicals originating from the peroxides. water and virtually no polymer dissolves in it, while most
This process runs at ambient temperatures, but generally monomers have a relatively high solubility in scCO2 . In ad-
takes days to weeks to reduce the amount of monomer to dition, relatively small changes in pressure and temperature
an acceptable level (Overbeek & Smak, 1993). can tune this solubility, the di4usion in scCO2 and the vis-
Stripping removes the residual monomer indirectly by cosity.
sweeping the aqueous phase with steam, gases or mixtures In this study, the emulsion polymerization of MMA has
of gases (Englund, 1981). It has been reported that stripping been taken as an example since MMA is an intensively used
combined with the addition of fresh free radical initiator to monomer in industrial emulsion polymerization. Previous
the latex has been carried out successfully (Taylor, 1985; work has shown that extraction is the predominant e4ect
Kelly, 1995). However, the foaming tendency and high vis- as compared to conversion of the monomer (Kemmere,
cosity of the latex are known to complicate the reactor de- van Schilt, Cleven, van Herk, & Keurentjes, 2002a). This
sign as they limit the rate at which the aqueous and gas is caused by the relatively high partitioning coe;cient
phases can be contacted, while a high contact area is of vi- between the CO2 and water phase, which indirectly deter-
tal importance to the viability of this technique. Moreover, mines the ratio between the e4ect of enhanced polymeriza-
the use of high temperatures might cause problems with the tion and extraction on the reduction of residual monomer.
colloidal stability of the latex as well as to the polymer mor- Depending on the various partitioning coe;cients involved
phology. In order to overcome the high-energy consumption in the system, this ratio between enhanced polymerization
bound to steam stripping, Olivares, Archundia, and Ramos and extraction may vary for other latex systems. Concern-
(1999) have reported a chemical depletion method based ing the PMMA/MMA latex system, the extraction capacity
on a redox system, which makes any additional steam strip- of CO2 has been quantiFed by measuring the partitioning
ping step redundant. A promising technique for residual behavior of MMA between the water and scCO2 phase in
monomer removal is pervaporation as no additional chemi- a high-pressure extraction unit with online sampling of the
cals are needed and the energy costs are typically low. It has aqueous phase. Based on the obtained results, a preliminary
been shown that pervaporation can remove a considerable process design has been developed for the removal of resid-
amount of acrylic monomer from polymethylmethacrylate ual monomer from latex products using scCO2 . For this
(PMMA) lattices (Keurentjes, Mills, & Kruizinga, 1993). purpose, a mass transfer model has been setup to determine
M. Kemmere et al. / Chemical Engineering Science 57 (2002) 3929 – 3937 3931

Table 1
Overview of various existing methods for removal of residual monomer from latex products

Technique Advantages Disadvantages

Temperature increase Simple to operate High energy costs


no toxic solvents required time consuming
Addition of an inert Simple to operate Removal of inert diluent required
diluent large reactor volume
Stripping No toxic solvents required Tendency to foam
Possible thermal degradation of
polymer
Colloidal instability of the latex
High throughputs of the stripping
Medium required
Pervaporation No additional separation step High membrane resistance
No toxic chemicals required High investment costs
No extra energy required Low 7uxes
Biological degradation Ambient temperature Time consuming
Large bath volumes
SpeciFc chemicals required

the rate limiting step in the extraction process. In addition,


an economic evaluation including equipment sizing has
been performed to study the viability of this technique for
removal of residual monomer.

3. Experimental

A high-pressure unit with on-line sampling of the aqueous


phase has been developed. Fig. 1 shows a schematic setup
of the equipment and a description of the relevant compo-
nents and features. With this equipment, the partitioning co-
e;cient m2 given by Eq. (1) was measured as a function of
pressure and temperature
[MMA]sc Fig. 1. Schematic view of the high-pressure lab-scale extraction equip-
m2 = : (1) ment (sample valve in sampling position) 1. Stainless steel high-pressure
[MMA]w equilibrium cell (64:33 ml), 2. Stainless-steel heating jacket, 3. Sample
line for extracting 7uid phase samples and venting valve, 4. Sample-line
The experimental procedure was started by adding a care-
for extracting light-phase samples and venting valve, 5. PT 100 tempera-
fully weighed amount of aqueous MMA solution into the ture sensor and miniaturized high-pressure transducer, 6. Magnetic stirrer
equilibrium cell Flling it for approximately 50%. The cell for 7uid phase agitation, 7. Equilibrium cell outlet, 8. 6-port HPLC sam-
was immediately sealed and heated to the desired temper- ple valve, 9. Calibrated 500 l sample loop, 10. Open connection for
ature. The liquid phase was stirred vigorously, creating a syringe, 11. Needle valve, 12. Chilled beaker containing glass vials for
sample collection, 13. Display of temperature and pressure, 14. Thermo-
deep vortex. At the desired temperature CO2 was introduced
static water heater, 15. Pulse-free 150 ml high-pressure syringe pump,
and pressurized by the high-pressure syringe pump. Equilib- 16. Cryostat for cooling the syringe pump.
rium was assumed if pressure and temperature did not vary
more than 0:2 bar and 0:2 K, respectively, within a period
In the proposed method the presence of only two phases
of 30 min. Then, a sample of the aqueous phase was taken
was assumed. Moreover, any signiFcant change of volume
by turning the HPLC-valve, the sample loop was depres-
of the phases was neglected. From the measured MMA con-
surized and led through the Frst tube of chilled methanol
centration in the aqueous phase at a certain pressure and
(MeOH) containing butanol as an internal standard, thus re-
temperature, the partitioning coe;cient can be calculated
moving the MMA from the sample. The second tube was
using Eq. (2). Here [MMA]w; 0 stands for the initial MMA
only used to verify whether no signiFcant amounts of MMA
concentration in the aqueous phase
have passed through the Frst tube. The contents of the Frst  
tube were analyzed by GC/FID in order to determine the [MMA]w; 0 Vw
m2 = exp − 1 : (2)
concentration of MMA. [MMA]w Vsc
3932 M. Kemmere et al. / Chemical Engineering Science 57 (2002) 3929 – 3937

Note that the initial MMA concentration is limited by the 4.2. Extraction model
solubility of MMA in water, whereas the experimental setup
restricts the Vsc =Vw ratio. In order to design an extraction unit, the rate limiting
step in the extraction process has to be determined. Three
phases are considered, i.e. the polymer, water, and scCO2
phase, respectively, whereas MMA is regarded as the di4us-
4. Results and discussion ing component, see Fig. 3. The Flm model has been used to
describe the extraction process, including the following as-
4.1. Partitioning coe5cients of MMA between water sumptions: (1) There occurs no mass transport of monomer
and CO2 directly from the polymer to the scCO2 phase. (2) The zones
for mass transfer resistances can be represented by two hy-
First, high-pressure view-cell experiments have been pothetical layers, in which the transfer is entirely determined
performed to study the phase behavior of the CO2 –H2 O– by molecular di4usion and the concentration gradient is lin-
MMA system at 298 K. Below 58 bar a two-phase system ear in each of these layers. (3) There is equilibrium at the in-
(CO2 (g); H2 O(l)) has been observed, whereas between 58 terfaces, so that the interface concentrations are determined
and 63 bar a three-phase region (CO2 (g); CO2 (l); H2 O(l)) by equilibrium conditions between the phases.
exists. This region has been omitted during the extraction Based on the overall transport 7ux of MMA from the
experiments. At 63 bar the beginning of the liquid–liquid polymer particles, via the aqueous phase to the supercritical
phase system (CO2 (l); H2 O(l)) has been observed. Similar phase, the overall mass transfer coe;cient (Kov; pol ) deFned
results have been described in detail by Adrian, Wendland, on the polymer phase is represented as a summation of the
Hasse, and Maurer (1998). resistances in the three phases, given by Eq. (3)
Considering the results of the extraction experiments per-
1 1 1
formed at 298 K shown in Fig. 2A, the partition coe;cient = +
increases signiFcantly above 63 bar. The increasing density Apolw kov; pol Apolw kpol Apolw kw m1
of the CO2 -rich phase at this point explains the sudden rise 1 1
of the partition coe;cient. Fig. 2B presents the measured + + : (3)
Awsc kw m2 Awsc ksc m1 m2
partition coe;cients at 313, 323 and 333 K, respectively.
View-cell experiments at 313 K show that three phases The partitioning coe;cients m1 and m2 , the mass transfer
resembling a boiling system can be distinguished close to coe;cients kpol , kw and ksc , the interfacial surface areas Apw
73–74 bar. This e4ect has not been observed at 323 or and Awsc have been determined in various ways as will be
333 K. In general, the system exhibits the same behav- discussed below.
ior at temperatures above the critical temperature of CO2 . In order to calculate the mass transfer coe;cient as
Around 50 bar all partition coe;cients are close to unity the di4usion coe;cient D divided by the di4usion length
and they increase with pressure. The rate of this increase Pz, the di4usion coe;cients of MMA in each phase have
gradually rises with pressure and decreases with temper- to be known. The di4usion coe;cient of MMA in the
ature. Similar to the results at lower temperatures, the polymer particles is determined using the Vrentas-Duda
partition coe;cient at 333 K is therefore expected to in- model, which is based on the free-volume theory (Faldi &
crease more signiFcantly beyond the measured pressure Tirrell, 1994). In general, the di4usion coe;cient of MMA
range. In general, these results can be explained by the in PMMA decreases with increasing weight fraction of
density of the CO2 -rich phase as it increases continu- polymer in the particles (Gilbert, 1995). Due to the plas-
ously with pressure above 74 bar. This e4ect is most pro- ticizing e4ect of scCO2 , however, the di4usion coe;cient
nounced at temperatures just above the critical temperature inside the polymer particles will be signiFcantly higher in
of CO2 . the presence of scCO2 than at atmospheric conditions. Few
In addition to the experimental data, the partitioning examples of the enhancement in di4usivity of components
behavior has been modeled using the Peng–Robinson equa- in polymers in the presence of CO2 have been reported.
tion of state (Peng & Robinson, 1976) combined with According to Chapman, Gochanour, and Pauliatis (1996),
the Panagiotopoulos–Reid mixing rule (Panagiotopoulos the di4usion coe;cient of solutes in a polymer can increase
& Reid, 1985) for which the interaction parameters used by at least 6 orders of magnitude in the presence of CO2
are given in Table 2. From an extensive comparison at subcritical pressures. In the extraction of ethylbenzene
of the calculations with the experimentally obtained re- from polystyrene using scCO2 , Alsoy and Duda (1998)
sults it can be concluded that the phase behavior of have reported an increased di4usivity of 2–3 orders of mag-
the ternary system MMA–H2 O–CO2 can adequately nitude as the weight fraction of CO2 increases 0% to 10%.
be correlated with the Peng–Robinson equation of Assuming that the di4usion coe;cient of MMA in PMMA
state in combination with the Panagiotopoulos– in the presence of CO2 is three orders of magnitude larger
Reid mixing rule (Kemmere, van Schilt, Jacobs, & than at atmospheric conditions, a value of approximately
Keurentjes, 2002b). 10−9 m2 =s is obtained.
M. Kemmere et al. / Chemical Engineering Science 57 (2002) 3929 – 3937 3933

Fig. 2. Measured and predicted partitioning coe;cients of MMA in water and scCO2 .

Table 2
Binary interaction parameters for the Panagiotopoulos–Reid mixing rule at di4erent temperatures used in the prediction of the phase behavior of the
ternary system MMA–H2 O–CO2

T H2 O–CO2 MMA–CO2 H2 O–MMA

(K) kij ij kij ij kij ij


298 0.170 0.304 −0.0556 0.280 −0.0459 0.254
313 0.173 0.286 −0.0669 0.217 −0.0293 0.255
323 0.184 0.286 −0.0744 0.175 −0.0174 0.258
333 0.201 0.286 −0.0819 0.133 −0.00485 0.261

The di4usion coe;cient of MMA in water has been es-


timated using the Wilke–Chang equation (Wilke & Chang,
1955)
1:173 × 10−16 w0:5 Mw0:5 T
Dw = 0:6
: (4)
VMMA

Using Eq. (4) a value of 1:9 × 10−9 m2 =s at 60◦ C is ob-


tained, for which the viscosity of the water is assumed to be
una4ected by the presence of scCO2 .
In literature some di4usion coe;cients of naphthol, naph-
thalene and phenanthrene in scCO2 are reported in the range Fig. 3. A schematic view of the three-Flm extraction model for the
of 2 × 10−8 –4 × 10−8 m2 =s (Abaroudi, Trabels, Calloud removal of residual monomer with scCO2 .
Gabriel, & Recasens, 1999; Madras, Thibaud, Erkey,
& Akgerman, 1994). The same order of magnitude is calcu-
lated for MMA in scCO2 (6:3 × 10−8 m2 =s at 60◦ C) using which the di4usion length is half the diameter of these par-
the empirical equation proposed by Fuller, Schettler, and ticles (Sh = 2; dp = 80 nm). The di4usion lengths in the
Giddings (1966) based on the corresponding states water and scCO2 phase are estimated to be 10 m, the char-
principle acteristic di4usion length in a laminar 7uid. The resulting
mass transfer coe;cients are given in Table 3.
Dsc (1 bar; 333 K) The partitioning coe;cient m1 , which is deFned as the
concentration MMA in the water phase divided by the cor-
0:00143T 1:75 0:5(1=MMMA + 1=MCO2 )0:5 responding concentration in the polymer phase, is given by
=  1=3  1=3 2 : (5)
P · [( v )CO + ( v )MMA ] Ballard, Napper, and Gilbert (1984). With respect to m2 , a
2
value of 5 has been taken as representative for the experi-
First the di4usion coe;cient is determined at 1 bar. Sub- mentally determined partitioning coe;cients shown in the
sequently, the di4usion coe;cient at higher pressures can previous section. The speciFc surface area of the polymer
be calculated using a function of the reduced pressure and particles is a function of the radius of the polymer particles
temperature. (rp ), the volume of latex relative to the volume of the to-
The di4usion length for mass transport in the polymer tal extraction volume, and the weight fraction of polymer
particles can be estimated from a worst case assumption in in the latex (!). This results in a speciFc surface area of
3934 M. Kemmere et al. / Chemical Engineering Science 57 (2002) 3929 – 3937

Table 3
Overview of the calculated mass transfer resistances in the scCO2 -extraction process of MMA from latex particles

Phase Resistance Parameters Time constant


(s)
1
Polymer respol = Dpol (m2 =s) 10−9
Apolw kpol
particles Pzpol (m) 4 × 10−8 3:77 × 10−6
kpol (m/s) 0.025
Apolw (m2 =m3 ) 1:06 × 107
1
Water at resw = Dw (m2 =s) 1:9 × 10−9
Apolw kw m1
polymer side Pzw (m) 1 × 10−5
kw (m/s) 1:9 × 10−4 7:43 × 10−3
Apolw (m2 =m3 ) 1:06 × 107
m1 (dimensionless) 0.067
1
Water at resw = Dw (m2 =s) 1:9 × 10−9
Awsc kw m1
scCO2 side Pzw (m) 1 × 10−5
kw (m/s) 1:9 × 10−4 39.4
Awsc (m2 =m3 ) 2000
m1 (dimensionless) 0.067
1
scCO2 ressc = Dsc (m2 =s) 6:3 × 10−8
Awsc ksc m1 m2
Pzsc (m) 1 × 10−5
ksc (m/s) 6:3 × 10−3 0.240
Awsc (m2 =m3 ) 2000
m1 (dimensionless) 0.067
m2 (dimensionless) 5

1:06 × 107 m2 =m3 . Considering the speciFc surface area be- scCO2 countercurrently. The start-up pump pressurizes the
tween the water and supercritical phase (Awsc ), an industri- CO2 from the supply tank (55 bar) to 80 bar. The scCO2
ally reasonable mass transfer area of 2000 m2 =m3 has been is conditioned by a heat exchanger (HEX1). The resid-
taken. With these data the resistance to mass transport in ual monomer is further polymerized and extracted from the
each phase can be calculated. According to Table 3, the polymer particles in the extractor at a pressure of 80 bar. A
largest resistance to mass transport is situated in the water controlled pressure relief will minimize foaming problems
phase at the scCO2 side. of the cleaned latex stream. The scCO2 and the residual
monomer are separated in a gas/liquid separator by reduc-
4.3. Process 8ow diagram and equipment sizing ing the pressure from 80 to 30 bar. As a consequence of
the adiabatic CO2 expansion the temperature will decrease
Fig. 4 shows the process design of the removal of resid- also. The extracted monomer can in principle be re-used in
ual monomer from 9000 to 100 ppm with scCO2 , calculated the polymerization process. The gaseous CO2 7ow from the
for a latex production of 30 kton=year (Cleven, 2001). As separation vessel is recycled to the extractor after pressur-
will be obvious from the previous section, an important is- izing by the recycle compressor and cooling to 60◦ C by a
sue in the process design is the selection of the extractor, heat exchanger (HEX2).
for which a high interfacial mass transfer area between the The di4erent process units are sized with general engi-
water and scCO2 phase is required. Mixer-settlers are ruled neering rules (Walas, 1990) as well as using simulations in
out as they contain less than one single mass transfer unit. the commercial process design package AspenPlus. It should
Towers with rotating stirrers cannot be used because of po- be noted that the calculated size of the extractor and separa-
tential fouling and a pulsed column has relatively high in- tor shown in Table 3 are relatively small as compared to the
vestment and operating costs and a limited throughput. In typical size of an industrial emulsion polymerization reactor
the current process design, a packed bed extractor is chosen, of 50 m3 . In contrast to most conventional techniques for
as it provides a high mass transfer area, lacks rotating parts, removal of residual monomer such as temperature rise, dou-
and has the possibility of a higher number of mass transfer bling the processing capacity would only require twice the
units depending on column height. extractor volume. Fig. 5 shows that in the case the permitted
The latex from the polymerization reactor (60◦ C) is fed amount of residual monomer in the product latex reduces to
to a packed bed extractor in which it is contacted with 10 ppm, less than doubling the extractor volume is needed.
M. Kemmere et al. / Chemical Engineering Science 57 (2002) 3929 – 3937 3935

Fig. 4. Process 7ow sheet for the removal of residual monomer from latex products using scCO2 .

Fig. 5. Sensitivity of the required extractor volume to the ppm requirements in the product latex and the partitioning coe;cient m2 .

In addition, an increase in partitioning coe;cient, m2 , with battery limits), plant overhead (80% of labor costs and 20%
a factor of 10 results in a decreasing extractor volume of maintenance) as well as capital charges (10 year deprecia-
approximately 20%. tion) are included in the calculations. As the infrastructure
is already present at the current polymerization plant, no ad-
4.4. Economic evaluation ditional costs are assumed to be made outside battery limits.
The operators on duty are assumed to handle the extraction
Based on the described process design, an economic fea- process, therefore no additional labor costs are made. The
sibility study has been performed. The total processing costs purchased costs of the process equipment shown in Table 4
are calculated from the costs of the process equipment, the are determined with the cost estimation program Chemical
chemicals and the utilities required. In addition, the start up Process Equipment Individual Equipment Costing (Walas,
costs (5% of total Fxed capital), maintenance (5% of inside 1990).
3936 M. Kemmere et al. / Chemical Engineering Science 57 (2002) 3929 – 3937

Table 4
Overview of purchased and installed costs per unit for the scCO2 -extraction process of residual monomer

Latex pump (stainless steel) Separator (vertical vessel)


Flow (m3 =h) 4.0 Height (m) 3.38
Head of feet 2592.0 Diameter (m) 1.12
Power (kW) 12.5 Wall thickness (m) 0.045
Purchased price 2000 ($) 10,500 Purchased price 2000 ($) 61,200
Installed costs 2000 ($) 21,000 Installed costs 2000 ($) 104,040

Start up pump (centrifugal, cast iron) Compressor (screw)


Flow (m3 =h) 3.45 Total power (kW) 53.66
Head of feet 995.7 Purchased price 2000 ($) 37,400
Power (kW) 3.44 Installed costs 2000 ($) 56,100
Purchased price 2000 ($) 19,100
Installed costs 2000 ($) 38,200

Heat exchange HEX1 (shell CS/tube SS) Heat exchanger HEX2 (shell CS/tube SS)
Heating duty (kW) 80.5 Heating duty (kW) (−) 51.57
U (W=m2 K) 850.0 U (W=m2 K) 850.0
Tm (K) 69.12 Tm (K) 57.00
Required area 1.4 Required area 4.52
Purchased price 2000 ($) 3,360 Purchased price 2000 ($) 4,150
Installed costs 2000 ($) 5,712 Installed costs 2000 ($) 7,055

Extractor (vertical vessel)


Height (m) 4.25
Diameter (m) 0.60
Wall thickness (m) 0.024
Purchased price 2000 ($) 30,000
Installed costs 2000 ($) 51,000

The calculated total capital required is approximately has been studied. Typically, the method comprises a
k$300. The calculated processing cost per ton latex is post-polymerization process in a counter7ow extraction ap-
approximately $4.70. The gas/liquid separator appears to paratus. From a mass transfer model, the largest resistance
have the largest Fxed cost. Optimizing the process con- to mass transfer in the extraction process appears to be
ditions in the separator results in a processing costs of situated in the water phase near the scCO2 interface due to
approximately $4.46/ton latex. Increasing the processing a relatively small interfacial area. Finally, a viability study
capacity to 63:4 kton latex a year and sharpening the per- based on a preliminary process design, including equipment
mitted amount of residual monomer in the product latex to sizing and economic evaluation, has shown that the removal
60 ppm, decreases the processing cost to $3.13/ton latex. of residual monomer from latex products using scCO2 is in
Taking into consideration the current production price of principle both technically and economically feasible.
latex (approximately $800/ton) the additional processing
cost for the new process are only 0.6% of the production
costs. Comparing the processing cost with conventional Notation
techniques to remove residual monomer is rather di;cult,
because no data of additional cost for the conventional tech- 
 viscosity of the solution, N s=m2
niques is available. Moreover, the costs for the removal of v di4usion volume, m3 =kmol
residual monomer depend signiFcantly on the properties of w association factor for water of water, di-
the produced latex. Taking into consideration the fact that mensionless
the conventional techniques are hardly able to meet more Pzx di4usion length, m
stringent requirements (e.g. 10 ppm residual monomer), [MMA] concentration methyl methacrylate,
the novel technique based on scCO2 is expected to become mol=m3
a viable alternative in the near future. [MMA]w; 0 initial concentration methyl methacrylate
in water phase, mol=m3
Ax speciFc surface area, m2 =m3
5. Conclusions dp polymer particle size, m
Dx di4usion coe;cient, m2 =s
The potential of a novel process for the removal of Kov; pol overall mass transfer coe;cient based on
residual monomer from latex-particles based on scCO2 polymer phase, m/s
M. Kemmere et al. / Chemical Engineering Science 57 (2002) 3929 – 3937 3937

kx mass transfer coe;cient (=Dx =Pzx ), m/s Englund, S. M. (1981). Monomer removal from latex. Chemical
Mx molecular weight, kg/kmol Engineering Progress, 55 –59.
m1 partitioning coe;cient of methyl Faldi, A., & Tirrell, M. (1994). Monomer di4usion and the kinetics
of methyl metacrylate radical polymerization at intermediate to high
methacrylate between, water and polymer
conversion. Macromolecules, 27, 4184–4192.
phase (=[MMA]w =[MMA]pol ), dimen- Fuller, E. N., Schettler, P. D., & Giddings, J. C. (1966). A new method
sionless for prediction of binary gas-phase di4usion coe;cients. Industrial and
m2 partitioning coe;cient methyl methacry- Engineering Chemistry, 58(5), 18–27.
late between, water and scCO2 phase Gilbert, R. G. (1995). Emulsion polymerization: A mechanistic approach.
London: Academic Press.
(=[MMA]sc =[MMA]w ), dimensionless
Kelly, P. (1995). Process for minimizing residual monomers. US Patent
P pressure, Pa 5430127.
Sh Sherwood number (=kx dp )=Dx ), dimen- Kemmere, M. F., van Schilt, M. A., Cleven, M. H. W., van Herk,
sionless A. M., & Keurentjes, J. T. F. (2002a). Reduction of residual monomer
T temperature, K from latex-products by enhanced polymerization and extraction in
supercritical carbon dioxide. Industrial and Engineering Chemistry
V volume, m3
Research, 41, 2617 – 2622.
VMMA molecular volume of MMA, m3 =kmol Kemmere, M. F., van Schilt, M. A., Jacobs, M. A., & Keurentjes, J. T. F.
(2002b) Measured and predicted partitioning coe;cients of methyl
Subscripts methacrylate between water and supercritical carbon dioxide, submitted
for publication.
Kendall, J. L., Canelas, D. A., Young, J. L., & DeSimone, J. M. (1999).
Pol polymer
Polymerizations in supercritical carbon dioxide. Chemical Reviews,
sc supercritical carbon dioxide 99, 543–563.
w water Keurentjes, J. T. F., Mills, E., & Kruizenga, F. J. (1993). Pervaporation of
acrylic monomers from latex dispersions. In Engineering Foundation,
new directions in separation technology. Noordwijkerhout.
Acknowledgements Madras, G., Thibaud, C., Erkey, C., & Akgerman, A. (1994). Modeling
of supercritical extraction of organics from solid matrices. A.I.Ch.E.
Journal, 40, 777–785.
Part of this work was supported by a grant from the Maxwell, I. A., Verdurmen, E. M. F. J., & German, A. L.
Foundation of Emulsion Polymerization (SEP) awarded to (1992). High-conversion emulsion polymerization. Makromolecular
Mascha Cleven. Chemistry, 193, 2677–2695.
Mayer, M. J. J., Meuldijk, J., & Thoenes, D. (1995). High conversion
emulsion polymerization in large scale reactors. Chemical Engineering
References Science, 50, 3329–3330.
Olivares, M. A., Archundia, F. J., & Ramos, F. L. (1999). Chemical
Abaroudi, K., Trabels, F., Calloud-Gabriel, B., & Recasens, F. (1999). depletion to substantially remove residual monomers in emulsion
Mass transport enhancement in modiFed supercritical 7uid. Industrial polymerization processes. US Patent 5886140.
and Engineering Chemistry Research, 38, 3505–3518. Overbeek, G. C., & Smak, Y. W. (1993). Removal of residual monomers
Adrian, T., Wendland, M., Hasse, H., & Maurer, G. (1998). High-pressure from polymers using peroxide-generating enzyme. European Patent
multiphase behavior of ternary systems carbon dioxide-water-polar 521620 (US 5292660).
solvent: Review and modeling with the Peng–Robinson equation of Panagiotopoulos, A. Z., & Reid, R. C. (1985). High-pressure phase
state. Journal of Supercritical Fluids, 12, 185–221. equilibria in ternary 7uid mixtures with a supercritical component.
Alsoy, S., & Duda, J. L. (1998). Supercritical devolization of polymers. ACS Division of Fuel Chemistry Preprints, 30, 46–56.
A.I.Ch.E. Journal, 44, 582–590. Peng, D., & Robinson, D. B. (1976). A new two-constant equation
Ballard, M. J., Napper, D. H., & Gilbert, R. G. (1984). Journal of of state. Industrial and Engineering Chemistry Fundamentals, 15,
Polymer Science, Polymer Chemistry Edition, 22, 3225–3253. 59–64.
Chapman, B. R., Gochanour, C. R., & Paulaitis, M. E. (1996). Poehlein, G. W. (1997). In J. M. Asua (ed.), Reaction engineering
CO2 -enhanced di4usion of azobenzene in glassy polystyrene near the for emulsion polymerization in polymer dispersions: Principles and
glass transition. Macromolecules, 29, 5635–5649. applications (pp. 305 –331). Dordrecht: Kluwer Academic Publishers.
Chen, S., & Lee, S. (1992). Limiting conversion for systems of Taylor, M. A. (1985). Chemical/steam stripping. US Patent 4529753
emulsiFer-free emulsion polymerization of styrene. Macromolecules, (EP 0158523).
25, 1530–1533. Walas, S. M. (1990). Chemical process equipment, selection and design.
Cleven, M. H. W. (2001). Removal of residual monomer from latex Stonehaun, MA: Butterworths-Heinemann.
products using supercritical carbon dioxide. Graduate Report in Wilke, C. R., & Chang, P. (1955). Correlation of di4usion coe;cients
Process and Product Design, Eindhoven University of Technology, in dilute solutions. A.I.Ch.E. Journal, 1, 264–270.
ISBN 90-444-0083-5.