TECHNICAL PAPER
ISSN 1047-3289 J. Air & Waste and
VOC Recovery through Microwave Regeneration of Adsorbents:
Process Design Studies
David W. Price and Philip S. Schmidt
Center for Energy and Environmental Resources, University of Texas at Austin, Austin, Texas
ABSTRACT
Process design studies are described for a new type of VOC
recovery system which uses microwave heating to regen-
erate adsorbents. Microwave regeneration systems create
a highly concentrated effluent from which the VOCs can
be recovered by condensation at near-ambient tempera-
tures. Important design considerations, predicated on
experimental work and model development, are identi-
fied and discussed. Parametric studies are then described
that identify the optimal adsorbent selection, operating
cycle, recovery configuration, regeneration pressure, re-
generation final coverage, and column configuration. In
general, it was found that microwave regenerated adsorp-
tion systems favor the use of low dielectric loss-factor
polymeric adsorbents and operation under low pressure
conditions (about 5 torr absolute pressure).
INTRODUCTION
One common method for VOC abatement consists of
passing the exhaust stream through a suitable adsorbent
to strip out organics, then regenerating the adsorbent to
concentrate the VOCs. Conventional regeneration of
adsorbents entails passing a hot gas, such as steam, air, or
nitrogen, upward through the bed. The stripping gas plays
the dual role of providing the necessary heat for desorp-
tion and sweeping the desorbed VOCs from the bed (main-
taining a low VOC partial pressure). However, the large
volume of stripping gas dilutes the concentration of VOCs
IMPLICATIONS
The emission of VOCs poses a serious environmental
control problem for many industries using organic solvents.
In particular, VOC emissions are of concern to the print-
ing, metal fabrication, plastics, semiconductor, and textile
industries. As restrictions on VOC emissions continue to
increase, there is a growing market for suitable control tech-
nologies. Most control systems presently employ destruc-
tive abatement techniques; relatively few options exist for
economic recovery and reuse of these valuable solvents,
particularly those that are water-soluble.
Volume 48 December 1998
Price
Manage. Schmidt
Assoc. 48:1135-1145
Copyright 1998 Air & Waste Management Association
in the effluent. Economical recovery is therefore prob-
lematic because low condensation temperatures are re-
quired in the case of hot gas stripping, or because a subse-
quent liquid separation step is needed with steam strip-
ping. Using microwave heating to regenerate adsorbents
may significantly enhance recoverability. Unlike conven-
tional regeneration methods, microwave regeneration
deposits heat directly and rapidly within the adsorbent
bed, producing a highly concentrated effluent so that the
VOCs can be easily recovered by condensation at near-
ambient temperatures.
During the 1980s a number of researchers investigated
the potential for using microwave heating to regenerate
adsorbents. Burkholder et al.1 found that applying micro-
wave energy enhances the desorption of ethanol from
silicalite because it selectively heats the ethanol without
heating the adsorbent. Furthermore, the researchers recog-
nized the possibility for using MW regeneration to facili-
tate solvent recovery. Singh2 examined the feasibility of
regenerating water from types 5A and 13x molecular sieves
in a domestic-type microwave oven. Roussy et al.,3 in an
experimental and theoretical study, concluded that water
molecules are desorbed from 13X molecular sieves directly
by the electromagnetic field; they found that the desorp-
tion kinetics were first order, varied with the square of the
electric field intensity, and were independent of the tem-
perature of the solid. Gibson et al.4 determined that micro-
wave heating reduced the desorption times of ethylene
oxide from polyvinyl chloride (PVC) by up to 400% over
conventional heating for the same macroscopic tempera-
ture. All of these studies, consisting of small laboratory set-
ups with test-tube quantities of adsorbents, were limited to
characterizing the heat-up and diffusion rates; they did not
address the applicability or feasibility of full-scale imple-
mentation of microwave regeneration processes.
The use of microwave heating to regenerate
adsorbents has been studied at the University of Texas at
Austin Center for Energy Studies since 1991. A series of
bench-scale experiments have shown that very high heat
transfer rates to the bed can be achieved, limited only by
the capacity of the microwave generator.5 Moreover, mass
Journal of the Air & Waste Management Association 1135
Price and Schmidt
transport out of the adsorbent is enhanced by a pressure-
driven flow (“expulsion”); in fact, the mass transfer rates
are so high that desorption follows a quasi-equilibrium
process.6 By contrast, conventional regeneration is typi-
cally rate-limited by heat and mass transfer resistance,
resulting in longer regeneration cycle times. This study
extends this body of work by addressing the technical fea-
sibility and identifying the most important process con-
siderations for a full-scale microwave regeneration plant:
adsorbent selection, column flow configuration, regen-
eration purge method, regeneration system pressure, and
final regeneration coverage.
OVERVIEW OF PROCESS MODELS
Two VOC emission streams were chosen as the basis for
study, typical of large-scale industrial printing operations,
an important area of application. In the first case, the
concentration and flow rate are representative of a plant
in which the VOCs are emitted into and collected from
the building permanent total enclosure (PTE flow condi-
tions: 144,000 cfm at 500 ppm). The second stream con-
tains the same volume flow of VOCs, but concentrated in
a much smaller air stream (22,500 cfm at 3220 ppm); this
is consistent with close-capture (CC) collection at the print
nip. The VOC was assumed to be methyl ethyl ketone
(MEK), a common industrial solvent with representative
dielectric and sorption properties.
Figure 1 overviews the set of process models devel-
oped to predict the performance of the adsorption and
regeneration cycles. First, relationships are developed for
the relevant dielectric, sorption, and thermodynamic
properties. Detailed knowledge of the sorption equilib-
rium behavior over the entire regeneration cycle is cru-
cial to accurately estimating the heating and purge re-
quirements for efficient desorption. The microwave des-
orption kinetics program is predicated on experimental
observations which indicate that the column follows a
quasiequilibrium process.6 An adsorption kinetics program
has also been developed following the method of
Michaels7 to predict the shape and location of the break-
through curves and the working capacity of the bed.
Figure 1. Modeling organization for microwave regeneration studies.
1136 Journal of the Air & Waste Management Association
Finally, the system process model incorporates the
output from these programs along with other relation-
ships to determine the overall performance characteris-
tics of the system. These include sizing calculations for
the adsorbent bed and other components as well as rela-
tions for determining pressure drop, blower requirements,
and power consumption of the microwave generators,
vacuum pumps, and refrigeration system. The model also
incorporates an economic analysis to estimate the capital
and operating costs of the individual equipment items
and the total plant based on vendor quotations and cor-
relations in the literature.
The underlying assumptions and methodology of the
economic analysis are discussed in detail by Price.8,9 Mi-
crowave generator costs are based on quotes from two
industrial generator suppliers for 50-75 kW, 915 MHz units.
Other microwave-related costs were estimated following
the procedure developed by Sanio and Schmidt.10 Oper-
ating costs are predicated on electric power rates of $0.059/
kWh for 5880 hr per year. In addition to the cost of elec-
tricity, the microwave operating costs include power tube
replacement at $0.031/kWh. Equipment costs for the re-
frigeration system, condenser, heat exchangers, vacuum
pumps, adsorption columns, and other equipment are
based on vendor quotes and correlations in the literature.
All costs are updated to January 1995 dollars using the
appropriate Chemical Engineering equipment cost indices.
Most of the studies discussed below focussed on the ap-
plication of hydrophobic adsorbents such as Dowex
Optipore (a polymeric adsorbent produced by Dow Chemi-
cal) and UOP Molsiv High Silica Zeolite (MHSZ).
SYSTEM CONFIGURATIONS
The most common types of adsorption systems employ
fixed-beds in batch operations. Here, the adsorbent remains
stationary in the column while the bed is cycled between
adsorption and desorption modes. Efficient desorption re-
quires two elements: heating to provide the necessary en-
ergy for desorption and to lower the equilibrium capacity
of the adsorbent, and purging of the desorbed VOCs to pre-
vent build up of the gas-phase concentration. For micro-
wave regeneration, adequate purge can be achieved by ei-
ther pulling a vacuum on the bed or flowing a purge gas
through it. Both methods reduce the concentration of VOCs
in the vapor-phase in the bed; for vacuum-purge regenera-
tion the desorption effluent is a pure solvent vapor stream
at low pressure while the stream is a mixture of inert and
VOC at ambient pressure for gas-purge regeneration.
Figures 2a-b show two possible solvent recovery con-
figurations for microwave regeneration systems operating
at low pressure. A large “dry” type (non-contaminating)
vacuum pump is used in Figure 2a to directly pull the
vacuum on the column. The desorbed VOCs are then
Volume 48 December 1998

condensed at ambient pressure with cooling water. A
precooler upstream of the vacuum pump cools the desorp-
tion effluent to near-ambient temperature in order to in-
crease the density and lower the operating temperature in
the pump. Figure 2b depicts a system where low pressure is
achieved by solvent condensation at low temperature. A
small vacuum pump is required for startup and for remov-
ing non-condensibles. The vacuum capability of the con-
denser is limited by the temperature of the coolant; for some
solvents, a small refrigeration system would be necessary.
The configuration decision strongly depends on the vapor
pressure curve of the solvent. For low-boiling solvents, such
as acetone (B.P. 56 °C at 1 atm), the vacuum-pump system
(Figure 2a) would be preferred, while less volatile solvents,
such as toluene (B.P. 110 °C), favor the refrigerated con-
denser configuration (Figure 2b).
For low concentration emission streams the adsorp-
tion cycle is much longer than desorption, so there are
typically multiple columns on-line adsorbing and a single
column being regenerated. Therefore, the desorption
modes would be staggered in such a way that the micro-
wave generator could be time-shared among the several
columns, thus maximizing its duty cycle and minimizing
generator capital costs.
An alternative method for removing the desorbed VOCs
from the bed is to sweep them out with a flow of inert gas
(Figure 2c). Because the stripping gas is not the primary
Figure 2. Microwave regeneration configurations: (a) vacuum-purge MW regeneration with a non-contaminating vacuum pump with atmospheric
pressure condensation, (b) vacuum-purge MW regeneration with a refrigerated condenser and auxiliary vacuum pump, and (c) inert-purge MW
regeneration with heat recovery and steam preheating.
Volume 48 December 1998
Price and Schmidt
heat source, much lower stripping gas flow rates can be
employed for MW regeneration than in conventional
regeneration. Air is not considered a suitable stripping
agent since the elevated VOC concentrations would
exceed the lower explosion limit. The inert gas at the
outlet of the condenser is saturated with VOCs and,
therefore, cannot be vented directly to the environ-
ment. It can either be sent to one of the on-line ad-
sorption columns before venting or recycled back to
the desorber as the purge gas stream. The first of these
two options is not attractive for two reasons. First, the
solvent content of this stream would still be relatively
high and readsorbing it would entail additional des-
orption stages, and second, the inert gas (probably ni-
trogen) is relatively expensive in large quantities and
must be recycled.
Incorporating a heat-recovery heat exchanger and
steam preheater reduces the microwave heating and refrig-
eration requirements for the inert-purge case. The gas-gas
heat exchanger serves the dual purpose of cooling the des-
orption effluent and preheating the inert recycled back to
the bed. Still, the recycled inert temperature is significantly
lower than the bed temperature, so a steam-preheater is
added to increase the temperature to about 100 °C. Both of
these devices are relatively inexpensive, but as will be shown,
they have a significant favorable impact on the operating
costs of the refrigeration and microwave subsystems.
Journal of the Air & Waste Management Association 1137
Price and Schmidt

There are important differences between Table 1. Comparison of performance and economics among vacuum and inert-purge microwave
regeneration systems for the PTE flow conditions (144,000 cfm at 500 ppm).
vacuum and inert purge with respect to the des-
orption thermodynamics, kinetics, and overall Vacuum Purge Inert Purge Inert Purge
system performance. Table 1 compares the per- (Figure 2b) With No Heat With Heat Recovery
Recovery (Figure 2c)
formance and economics of vacuum purge re-
generation (Figure 2b) and inert-purge regenera- Adsorbent Optipore Optipore Optipore
tion with and without heat recovery. The PTE Adsorbate MEK MEK MEK
flow conditions were assumed and the key oper- Condensation temperature (°C) -26 -26 -13
Pvoc at bed inlet (torr) 5 5 12
ating variables (condensation temperature, inert P at bed outlet (torr) 5 45 38
voc
flow rate, and final regeneration temperature) Nitrogen flow/VOC flow (kg/kg) — 6.9 10.6
were chosen based on separate optimization stud- Final regeneration temperature (°C) 120 150 150
Microwave power consumption (kW) 243 387 277
ies for each configuration. The levelized cost per
Recovery system power (kW) 111 250 100
pound of treated solvent (COS) in Table 1 reflects Makeup nitrogen costa ($/yr) — 260,000 260,000
b
the total cost of ownership, including both capi- Total capital investment ($) 3,063,000 3,333,000 3,159,000
Adsorption subsystem cost ($) 1,129,000 1,129,000 1,129,000
tal and operating costs, and is normalized based
Adsorbent inventory ($) 1,335,000 1,335,000 1,335,000
on the annual mass of treated solvent. Microwave system cost ($) 403,000 607,000 451,000
The results indicate that vacuum-purge of- Recovery system cost ($) 196,000 263,000 245,000
c
fers substantial performance and economic ben- Total operating costs d ($/yr) 472,000 882,000 762,000
Levelized cost (COS) ($/lbm VOC) 0.206 0.303 0.271
efits for MW regeneration. Most importantly, the
vacuum-purge system has a lower microwave a Makeup nitrogen costs are predicated on the fact that at the beginning of each desorption cycle, the volume
power consumption since, for a given conden- of b
air in the column must be displaced with inert.
The total installed cost of the system.
sation temperature, there is a lower average va- c
Include all utilities, operating and maintenance costs, overhead, property taxes, insurance, and administra-
por-phase concentration in the bed. That is, the tive costs.
d
vacuum pulled by the condenser at a given con- The levelized COS reflects the total cost of ownership, including both capital and operating costs. To
densation temperature establishes a uniform VOC calculate the levelized cost ($/lbm VOC), the capital costs are annualized using a capital recovery factor of
16.28% (10-year equipment life at a 10% interest rate) and added to the annual operating costs. This total
partial pressure in the bed at the corresponding annual cost ($/yr) then is divided by the total mass of treated solvent per year.
saturation pressure. On the other hand, if the
same condenser temperature is available for an
inert-purge system, this partial pressure is maintained only OPTIMAL REGENERATION PRESSURE
at the inlet; the desorbed VOCs increase the concentra- For vacuum-purge batch MW regeneration systems, the
tion of VOCs in the inert stream with bed height. Con- pressure is perhaps the most significant process variable
sequently, the sorption equilibrium curves indicate a since it strongly affects desorption thermodynamics and
higher final regeneration temperature and higher micro- kinetics as well as the size and power consumption of the
wave power consumption for the inert-purge system to recovery system. Lowering the pressure demands larger
achieve the same degree of regeneration. This effect is, vacuum pumps that consume more power. However, mi-
in fact, large enough to outweigh the effect of supple- crowave power consumption and generator capacity both
mental steam heating. decrease since reducing the pressure lowers the final tem-
The cost of the adsorbent inventory, adsorption perature to which the bed must be heated to achieve a given
columns, and recovery system are roughly the same degree of reactivation. Because the system pressure affects
for the three cases. Most of the variation in capital cost the performance of both the desorption and solvent recov-
stems from the microwave system cost, which is pro- ery subsystems, the total impact can only be assessed by
portional to the power consumption. The inert-purge examining the total system performance and economics.
configurations also require a much larger condenser Figure 3 plots the cost per unit of recovered solvent as
because of the higher film resistance caused by the a function of regeneration pressure for both of the vacuum-
inert. The operating costs resulting from the make-up purge configurations described previously. The very clear
nitrogen and the higher microwave and refrigeration decrease in system cost with decreasing pressures reflects
power are mostly responsible for the higher cost of re- the fact that mechanical vacuum pump energy is generally
covered solvent. By adding heat recovery and steam cheaper and has a stronger effect on desorption equilibria
preheating to the inert purge configuration, both the than microwave heating. This variation in system cost with
microwave generator and recovery system power con- pressure apparently stems entirely from the difference in
sumption are reduced substantially. The remaining equipment costs between microwave and vacuum produc-
studies will focus on vacuum-purge regeneration since tion equipment, per unit of power; the sum of the operat-
it is clearly the more attractive configuration. ing costs associated with the vacuum pump and microwave

1138 Journal of the Air & Waste Management Association Volume 48 December 1998

0.25
0.24
Levelized Cost, COS
0.23 Refrigeration
($/lbm)
System
0.22
Vacuum Pump
0.21
0.2
0 20 40 60 80 100
System Pressure (torr)
Figure 3. Optimal regeneration pressure level for vacuum-purge MW
regeneration.
generator power consumption does not appreciably change
with pressure. Furthermore, regenerating at lower pressures
implies lower final heating temperatures; this makes the
process less likely to thermally damage the solvent.
It appears that using a vacuum pump is slightly more
attractive than a refrigerated-condenser at all but the low-
est pressures for MEK. However, dry-type vacuum pumps
are generally not available as single units for flow rates
exceeding 12,000 acfm, which corresponds to the given
mass flow of VOC at 5 torr. The sharp increase in the sys-
tem cost at 1 torr stems from the necessity of purchasing
four separate vacuum pumps (cost exponent of 1) as op-
posed to simply increasing the capacity of a single pump
(typical cost exponent of 0.45).
Figure 3 suggests that further reduction in pressure
would be cost-effective for the refrigerated condenser sys-
tem. However, at pressures below 1 torr the condensation
temperatures become extremely low for MEK and other
low boiling solvents. Also, further reducing the final re-
generation temperature by lowering the pressure reduces
the microwave heating rate and, therefore, may eventu-
ally shut down the microwave-enhanced mass transfer
effects and the quasi-equilibrium process observed in the
experimental studies. For example, a 1 torr regeneration
pressure corresponds to a final heating temperature of only
90 °C. Therefore, the optimal pressure for vacuum-purge
microwave regeneration is probably in the 1–5 torr range
for MEK. While these results were for MEK on Dowex
Optipore at the PTE flow conditions, the same trends have
been observed in calculations for the MHSZ adsorbent and
with other solvents under different flow conditions.
OPTIMAL FINAL REGENERATION COVERAGE
Once the regeneration pressure has been selected, the
degree to which the adsorbent is regenerated depends only
on the final heating temperature. Because of the high unit-
cost of microwave energy relative to conventional energy
sources (e.g., steam), this selection strongly affects the
Volume 48 December 1998
Price and Schmidt
overall system economics. Moreover, there are several in-
herent differences in the bed dynamics between micro-
wave and conventional regeneration.
In conventional regeneration systems, it is seldom
economical to completely reactivate the bed. First, these
systems exhibit distributed moving heat and mass trans-
fer zones. As the fronts of these zones approach and break
through the top of the bed, an increasing portion of the
stream’s heat content is thrown away. Therefore, desorp-
120 140 tion is typically terminated soon after the leading edge of
the zone breaks through the top of the bed, leaving a
“heel” of partially unregenerated bed. Furthermore, com-
plete regeneration of the bed for conventional adsorbents
such as activated carbon and molecular sieves frequently
requires gas temperatures in excess of 250 °C, particularly
for high-boiling organics. Low-pressure steam, the most
common stripping agent, is generally not available at tem-
peratures above 200 °C. This problem is compounded by
the fact that the heat of desorption increases sharply at
low coverage.
Experimental studies have demonstrated that it is
much more attractive to fully regenerate the bed for
vacuum-purge microwave regeneration. First, the micro-
waves heat the entire bed volumetrically while the vacuum
pump maintains a uniform gas pressure. Consequently,
there are no moving heat and mass transfer zones and
the bed can be efficiently desorbed to completion. Fur-
thermore, high bed temperatures are readily achieved with
microwave heating since there is no limiting heat source
temperature. Finally, process conditions suggest that it
may be desirable to regenerate the bed to near-comple-
tion in order to minimize the possibility of early break-
through in the subsequent adsorption cycle.
Figure 4 plots the microwave generator power re-
quirement as a function of final coverage. As will be
discussed later, the microwave power consumption is
a strong function of the working capacity of the ad-
sorbent; regenerating the adsorbent more fully (lower
coverage) increases the desorption efficiency by put-
ting more energy into the desorption phase change
and less into the sensible heat of the bed. The results
shown in Figure 4 correspond to the PTE case flow
conditions, but the same trends are seen for other flow
conditions. Note that while the lower pressure curves
reflect lower microwave power requirements, the power
consumption of the vacuum pump and/or refrigera-
tion system are correspondingly higher. Thus, opera-
tional and process considerations suggest that the
Dowex Optipore and MHSZ adsorbents should be re-
generated to near-zero coverage. Consequently, a low
enough pressure should be chosen so that the corre-
sponding final regeneration temperature does not ex-
ceed the temperature limit of the adsorbent.
Journal of the Air & Waste Management Association 1139
 Price and Schmidt
1000
MW Generator Power (kW)
150 torr
800
25 torr
600
10 torr
400
200
0 phobicity— only adsorbing water at high relative humidi-
0 2 4 6 8 10
Coverage
(g MEK/100 g adsorbent)
Figure 4. Optimal final regeneration coverage for vacuum-purge
regeneration at different regeneration pressures.
ADSORBENT SELECTION
Choosing an appropriate adsorbent is one of the most
important process decisions for VOC recovery systems,
either conventional or microwave-regenerated. In many
ways, it dictates the performance of both adsorption and
desorption cycles. This study considers four adsorbents
commonly employed for adsorbing volatile organic com-
pounds from waste air streams: Dowex Optipore 11,12 (a
hydrophobic, polymeric adsorbent produced by Dow
Chemical), UOP hydrophobic Molsiv High Silica Zeolite
(MHSZ),13,14 Calgon BPL activated carbon,15 and Grace/
Davison molecular sieve 13x.16
Tables 2 and 3 list some of the properties and perfor-
mance of these four adsorbents operating in low and high
VOC (MEK) concentration air streams, respectively. These
cases studies were conducted for vacuum-purge microwave
regeneration at a pressure of 25 torr in order to corre-
spond with the available lab data for the different
adsorbents.6 Although unit costs of the MHSZ and Dowex
Optipore adsorbents are considerably higher than the
molecular sieve and activated carbon, a more relevant
number is the cost per unit of adsorbed VOC, which takes
into account the sorptive capacity. The high cost of the
Dowex Optipore polymeric adsorbent is, in part, balanced
by the fact that its resilience is expected to give it a longer
lifetime than the three years typical of the other adsorbents
in VOC removal service.11,13,17
The relative performance of each of these adsorbents
from the sorption, process, and dielectric heating perspec-
tives is discussed below. Because the adsorbent affects the
performance of virtually every plant component, the true
effect can be gleaned only by examining the total system
performance and economics.
Sorption Considerations
First, the adsorbent must possess the selectivity to adsorb
the VOC(s) of interest while allowing environmentally
1140 Journal of the Air & Waste Management Association
benign species to pass through the bed. Since most ad-
sorption applications involve humid gas streams (e.g.,
ambient air) it is necessary to either choose hydrophobic
adsorbents or make provisions for dehydrating the stream;
excessive water adsorption hampers performance by rap-
idly depleting the adsorbent’s capacity, wasting regenera-
tion energy to desorb the water, and producing a recov-
ered solvent with a high water content. The Dowex
Optipore and MHSZ adsorbents exhibit excellent hydro-
ties. Activated carbon is moderately hydrophobic, but
exhibits a dramatic increase in its affinity for water at rela-
tive humidities over 50%. Molecular sieve 13X is hydro-
philic and only applicable for dry gas streams or in pro-
cesses where the moisture has been removed upstream
using, for example, a rotary desiccant wheel.
Tables 2 and 3 also list the equilibrium sorptive capaci-
ties for MEK at low and high VOC concentrations, respec-
tively. Dowex Optipore and activated carbon both exhibit
relatively high sorptive capacities for MEK— about twice
that of MHSZ and MS 13X. The actual capacity of the bed,
however, depends in part on the sharpness of the isotherm
and the adsorbent’s kinetic performance. Dynamic adsorp-
tion occurs in a mass transfer zone with a finite length.
When the leading edge reaches the top of the bed, the col-
umn must be regenerated despite the fact that much of the
capacity of the adsorbent in the mass transfer zone is not
utilized. Dowex Optipore and MHSZ exhibit much better
kinetic performance (i.e., very steep isotherms and high
mass transfer rates) and therefore a shorter mass transfer
zone than the molecular sieve and activated carbon
adsorbents. The values for the equilibrium sorptive capaci-
ties in these tables correspond to a low humidity environ-
ment (i.e., less than 40% relative humidity).
The other factor that dictates the working capacity of
the adsorbent is the regenerability. While the Dowex
Optipore and MHSZ may be easily regenerated to comple-
tion, much higher temperatures are required to completely
desorb polar solvents from activated carbon and molecular
sieves. In practice, it is not economical to completely re-
generate these adsorbents. Thus, the actual “working ca-
pacity” of the adsorbent is diminished considerably from
the theoretical equilibrium capacities listed in Tables 2 and
3. Activated carbon, for example, typically has a working
capacity of about half of its equilibrium capacity.18
Process Considerations
One of the largest operating costs stems from the power
requirements of the system fans. While increasing the
adsorbent particle size reduces the pressure drop across
the bed, it also increases the mass transfer resistance and,
therefore, reduces the working capacity of the adsorbent.
Table 2 lists the pressure drop for each of the adsorbents.
Volume 48 December 1998
 Price and Schmidt

The average particle size used in this analy- Table 2. Effect of adsorbent selection for the PTE flow conditions (144,000 cfm @ 500 ppm). a,b
sis is 1.5 mm for the Dowex Optipore and 3
Dowex Activated Molecular
mm for the others. In this study, a bed depth Optipore MHSZ Carbon Sieve 13X
of 1 ft was used for the Dowex Optipore and
Adsorbent unit cost ($/lbm adsorbent) 25.00 7.10 2.50 2.50
MHSZ adsorbents because of the high unit
Specific adsorbent cost ($/lbm MEK) 192 101 17 36
cost and short length of the mass transfer Equil. coverage (g MEK/g adsorbent) 0.13 0.07 0.15 0.07
zone; a bed depth of 1.5 ft was more suit- Pressure drop/ft of bed (in. H2O/ft) 12.2 5.0 4.1 8.7
able for the other two adsorbents because System fan power (kW) 343 140 171 366
Specific heat (kJ/kg K) 1.26 0.84 1.05 1.00
of their lower unit cost and larger mass trans- Heat of desorption (kJ/kg) 576 662 752 814
fer zone. As shown in the tables, the system Final regen. temp. (°C) (coverage) 150 (0.00) 193 (0.01) 360 (0.05) 350 (0.01)
fan power is directly proportional to the Specific microwave heat (kJ/kg MEK) 2,071 3,276 6,139 8,575
Microwave generator power (kW) 298 537 1,038 1,840
pressure drop and air flow rate.
Total capital investment ($) 3,039,000 2,549,000 3,015,000 4,268,000
The variation in system fan power is Annual operating costs ($/yr) 477,000 718,000 936,000 1,459,000
rather small compared to the variation in Levelized cost, COS ($/lbm VOC) 0.207 0.223 0.295 0.445
microwave power with adsorbent selection. a
These parameters are based on the available sorption isotherms from the adsorbent manufactures, microwave
All of the microwave heating essentially regeneration experimental data, and the sorption equilibria models.
b
ends up in two places: sensible heat of the The process flow diagram for these systems is shown in Figure 2b.
bed (and VOC) and latent heat of desorp-
tion. The bed and VOC sensible heat is basi- Table 3. Effect of adsorbent selection for the CC flow conditions (22,500 cfm @ 3,220 ppm).a
cally “wasted” energy; it must eventually be
removed in the bed cooling step prior to Dowex Activated Molecular
Optipore MHSZ Carbon Sieve 13X
adsorption and by the cooling water in the
condenser. The microwave power consump- Specific adsorbent cost ($/lbm MEK) 104 55 11 19
tion is a complex function of several vari- Equil. coverage (g MEK/g adsorbent) 0.24 0.13 0.22 0.13
System fan power (kW) 39 14 20 42
ables:
Specific microwave heat req.
(kJ/kg MEK) 1,483 2,133 4,117 4,927
(1) Adsorbent/VOC Heat Capacity. For Microwave generator power (kW) 197 302 620 804
a given final regeneration tempera- Total capital investment ($) 1,321,000 1,197,000 1,578,000 1,878,000
Annual operating costs ($/yr) 239,000 357,000 535,000 666,000
ture, adsorbents with large specific Levelized cost, COS ($/lbm VOC) 0.097 0.116 0.166 0.202
heats require more microwave
a
power. Identical information from Table 2 is not repeated.
(2) Final Regeneration Temperature.
The microwave power and system economics at 500 ppm the molecular sieve requires 8575 kJ
depend strongly on the temperature to which the of microwave heating per kg of desorbed MEK
adsorbent must be heated to achieve the desired compared to only 4927 kJ/kg at 3220 ppm.
degree of regeneration for the given vacuum con- The Dowex Optipore adsorbent has all of these factors
ditions. When comparing different adsorbents, working in its favor. Its high equilibrium capacity and small
it is crucial to employ the optimal final regen- mass transfer zone give it the largest working capacity of
eration coverage. the four adsorbents. It also has the lowest heat of desorp-
(3) Heat of Desorption. Roughly half of the micro- tion and final regeneration temperature. These factors com-
wave heating is consumed by the latent heat of bine to give it the lowest specific microwave heating re-
desorption. Table 2 indicates that there is signifi- quirement. The MHSZ, while having a low equilibrium
cant variation in this value among the four capacity, has a moderately high working capacity because
adsorbents. of its sharp isotherms; it also has low heat of desorption,
(4) Working Capacity. The lower the adsorbent work- heat capacity, and final regeneration temperature. The
ing capacity, the higher the ratio of bed sensible carbon adsorbent has a moderate working capacity, but
heat to latent heat of desorption. That is, more requires high regeneration temperatures and has a high
adsorbent must be heated up to desorb the same heat of desorption. Molecular sieve 13X has all of these
amount of VOC. The effect of the working ca- factors working against it: low working capacity and high
pacity alone can be examined by comparing the heat of desorption, specific heat, and final regeneration
specific microwave heating requirement for a temperature. As a result, six times more microwave heat-
given adsorbent between the high and low VOC ing is required than for Dowex Optipore.
concentration cases (Tables 2 and 3). For example, Tables 2 and 3 also summarize overall system

Volume 48 December 1998 Journal of the Air & Waste Management Association 1141
Price and Schmidt

economic parameters for the prototypical fixed-bed sys-
tems. As shown, the economics are very sensitive to the
microwave generator capacity, so the Dowex Optipore,
while 10 times more expensive (per unit), yields the most
cost-effective system. The effect of VOC concentration in
the feed stream can be seen by comparing the results from
Table 3 with that from Table 2. While the performance is,
in general, better for the CC case because of the higher
sorptive capacities, the same trends appear.
Process safety considerations may also restrict the use
of certain adsorbent/VOC combinations. For example, ke-
tones, aldehydes, and organic acids can react exothermi-
cally on activated carbon adsorbents, possibly leading to
bed fires. Finally, if microwave heating non-uniformities
occur, it may be possible to mix these out by intermittently
fluidizing the bed during the desorption cycle. Dowex
Optipore’s resilience and resistance to attrition make it par-
ticularly attractive if such a scheme is employed.
Dielectric Considerations
The property that describes how well a material absorbs
microwave energy and converts it into heat is the dielec-
tric loss factor (ε”). In general, the heat-up rate of a mate-
rial in an applied electric field is proportional to the di-
electric loss factor, frequency, and the square of the
strength of the electric field inside the material. The pen-
etration depth (δ), defined as the distance from the sur-
face of the bed at which the power decays to 1/e of its
value at the surface, is inversely proportional to the di-
electric loss factor20
λ0 ε'
δ=
2πε"
heating takes place in this area. Thus, heating non-unifor-
mities are, to some degree, self-correcting in a manner analo-
gous to “moisture leveling” in drying applications. Table 4 il-
lustrates the variation in loss-factor and penetration depth
among adsorbents for MEK adsorption.
Finally, the selection of an adsorbent may also be in-
fluenced by the dielectric properties of the solvent. For
example, if a very low loss-factor solvent is to be regener-
ated, an adsorbent with a high loss-factor might need to
be chosen in order to achieve reasonable bed heat-up rates.
In short, while the polymeric and high-silica adsorbents
are considerably more expensive, they exhibit superior
sorptive performance and their dielectric properties make
them more suitable for microwave heating.
COLUMN CONFIGURATION
The configuration of the adsorption column for fixed-bed
systems represents the heart of the design problem since
it must satisfy both sorption and electromagnetic con-
straints. Figure 5 illustrates the electromagnetic and gas
flow regimes for three possible column configurations:
axial-flow columns, horizontal columns with an internal
rectangular bed, and radial-flow columns. For axial or
horizontal-bed configurations, the feed stream is usually
directed downward through the bed during adsorption
in order to prevent fluidization of the adsorbent particles
at the high velocities typical of adsorption. Counter-cur-
rent flow during regeneration (upward) prevents
readsorption in the unsaturated bottom portion of the
bed.21 In radial-flow columns, the adsorbent is held in
the annular space between the two cylinders. The follow-
(1) ing discusses some of the important design considerations
for column selection.

Here, λ0 is the wavelength of the radiation in free space, ε’ Flow Uniformity

is the dielectric constant, and ε” is the dielectric loss factor. A non-uniform air flow distribution can result in portions
Experimental studies have indicated that the dielec- of the bed that are unsaturated or lead to early break-
tric loss-factor of the adsorbent dominates the heat-up rate through. This has a negative effect on the operating costs
when regenerated with microwaves.6 However, eq 1 sug- since the bed must be regenerated more frequently. Axial
gests that adsorbents with very high loss-fac-
tors, such as activated carbon, exhibit short Table 4. Comparison of the dielectric loss factor a (ε”) and penetration depthb (δ) among dry and saturated
penetration depths, making it difficult to (MEK) adsorbents.
uniformly heat a large bed of material. For
this reason, it may be more attractive to Adsorbent ε”dry ε”sat δdry δsat δdry δsat
employ adsorbents with low loss-factors, 2,450 MHz 2450 MHz 915 MHz 915 MHz
such as Dowex Optipore and MHSZ. Roy and (cm) (cm) (cm) (cm)

Schmidt indicate that for such adsorbents,

Molecular sieve 13X 0.25 0.25 15 15 39 39
the loss factor of the bed becomes a strong
Dowex Optipore 0.03 0.24 103 13 276 34
function of the concentration of solvent on
High silica zeolite 0.03 0.15 120 24 324 64
the adsorbent.19 When the bed is saturated,
the bed has a high loss factor; but as the VOC a The loss factor was measured at 2,450 MHz and assumed to not change significantly at 915 MHz.19
is driven off a portion of the bed, the local b The penetration depth is defined as the distance from the surface of the bed at which the power decays to 1/e of
loss-factor decreases and little additional its value at the surface.

1142 Journal of the Air & Waste Management Association Volume 48 December 1998

and horizontal-bed columns both exhibit excellent flow
uniformity, but there are several potential sources for flow
maldistribution in radial flow columns:22-24
(1) Flow Bypass. Some empty space must be left in
the top of the column to provide for backwashing
and adsorbent swelling. The feed stream may
tend to bypass the bed and flow through this
empty space, resulting in poor bed utilization or
early breakthrough.
(2) Channeling. Flow may tend to favor either the
top or the bottom of the bed if the pressure gra-
dient across the bed is not uniform. It is relatively
difficult to achieve a uniform pressure gradient in
radial-flow columns because the finer adsorbent
particles settle toward the bottom, resulting in a
higher packing density (lower permeability).
(3) Fluidization. Typical adsorption velocities are on
the order of the minimum fluidization velocity
for smaller adsorbent particles. For radial-flow
columns, the velocity is even higher at the inner
annulus. Fluidization is avoided with axial and
horizontal-bed columns by directing the flow
downward through the bed.
(4) Bed Swelling. As the bed rises due to swelling,
the top of the bed will move relative to the loca-
tion of the top row of flow holes on the inner
annulus. This will result in poor utilization of
the top layers of the bed.
Electromagnetic Considerations
During microwave regeneration, non-uniformities in elec-
tric field distribution will result in bed hot spots and, con-
sequently, incomplete or inefficient regeneration. To mini-
mize the effect of field strength decay, the microwaves
will be applied in the direction of the smallest bed di-
mension. One possibility for the axial and horizontal-bed
columns, is to use the entire column as a multimode cav-
ity and direct the microwaves into the bed from both the
top and bottom; the bed support structure would be con-
structed out of fiberglass, alumina, or some other micro-
wave-transparent material. For radial-flow columns, it may
be attractive to employ a leaky waveguide applicator; di-
recting the microwaves radially-inward would balance the
decay in the electric field intensity with decreasing cross-
sectional area. However, locating a discrete number of
applicators around the periphery might produce hot-spots
due to the irregular geometry, constructive/destructive
interference of the waves, and high field intensities near
the waveguide slots.
Column Cost
The size and number of columns required for adsorption
is dictated by the volumetric flow rate of air to be treated.
Volume 48 December 1998
Price and Schmidt
The bed area perpendicular to the flow is the air flow rate
divided by the superficial velocity through the column.
Pressure drop and residence time constraints limit the
superficial velocity to 75–100 ft/min while transportation
limitations restrict column sizes to about 12 ft in diam-
eter and 30 ft in length.18 A 144,000 cfm VOC emission
stream (PTE conditions) at a superficial velocity of 85 ft/
min would require a total of 6 horizontal-bed columns,
17 axial-flow columns, or 9 radial-flow columns. Thus,
for large flow rate systems such as those considered in
this study, horizontal-bed columns are usually recom-
mended.17,25 The number of required columns is impor-
tant not only because of the large capital cost per column,
but also because of the added cost of associated microwave
delivery components (waveguide, applicator, etc.).
While radial-flow columns have been applied exten-
sively for applications such as methanol synthesis, cata-
lytic reforming, desulfurization, and catalytic mufflers,
they have not been particularly successful for adsorption
applications. Kovach states that annular beds have been
designed but have seen only limited use because of high
attrition losses.25 They also have more severe structural
problems due to the increased stress acting on the adsor-
bent which settles to the lower end of the column while
the bed expands and contracts in successive adsorption/
desorption cycles. Because of the large air flow rates, the
inner annulus will have to be about 2 ft for a bed flow
rate of 12,000 scfm.
CONCLUSIONS
Design studies were conducted for several process configu-
rations to evaluate the effects of various design and operat-
ing parameters on the performance of fixed-bed MW re-
generation systems for VOC recovery. Computer models
were developed to simulate the performance of various MW
regeneration configurations and systematically investigate
the effects of the following key operating variables on per-
formance and economics: adsorbent selection, column flow
configuration, regeneration purge method, regeneration
system pressure, and final regeneration coverage. Table 5
presents the optimal set of operating conditions for the PTE
and CC flow conditions, respectively.
While the cost of the adsorbent inventory is a large
percentage of the total system cost, the high capacity and
ease of regeneration of the Dowex Optipore and MHSZ
adsorbents make them the most cost-effective. Both
adsorbents are presented as optimal cases because their
performance and economics were nearly the same. Acti-
vated carbon and conventional molecular sieves are con-
siderably less expensive, but the high desorption tempera-
tures, heats of desorption, and low working capacities
entail several times more microwave power consumption.
The Dowex Optipore and MHSZ adsorbents are also more
Journal of the Air & Waste Management Association 1143
Price and Schmidt

attractive from the operational viewpoint Table 5. Optimal plant configuration and operating variables for fixed-bed, vacuum-purge microwave regener-
because they are hydrophobic and com- ated adsorption system (Figure 2a) under both PTE and CC flow conditions.
pletely non-reactive. Carbon is moderately
hydrophobic but impurities within it can PTE Flow CC Flow
144,000 cfm, 500 ppm 22,500 cfm, 3,220 ppm
catalyze exothermic reactions with ke-
tones. Molecular sieves are hydrophilic
Dowex MHSZ Dowex MHSZ
and, therefore, not suitable for this appli-
Optipore Optipore
cation. The polymeric and high-silica
adsorbents also possess relatively low di- Purge method Vacuum Vacuum Vacuum Vacuum
electric loss-factors which implies longer Regeneration pressure (torr) 5 5 5 5
microwave penetration depths and there- Final regeneration coverage 0.00 0.00 0.00 0.00
fore more uniform heating. Final regeneration temp. (°C) 120 150 120 150
Large air flow systems favor horizon- Column configuration Horiz. bed Horiz. bed Horiz. bed Horiz. bed
tal-bed columns beds since they present a Total number of columns 6 6 2 2
larger cross-sectional area and, therefore, Bed height (ft) 1 1 1 1
fewer columns are necessary. This reduces Bed superficial velocity (ft/min) 85 85 85 85
Pressure drop (“H2O) 12.2 5 8.8 3.3
the system complexity and lowers the
Cycle times: ads/reg/cool (hr) 6.4/1.1/0.13 4.7/0.7/0.13 2.4/2.1/0.16 1.7/1.5/0.17
capital and installation costs of not only
Microwave generator capacity (kW) 243 368 168 235
the columns and gas piping, but also the
Microwave power consumption (kW) 254 355 189 252
microwave power delivery components. System fan power (kW) 343 140 39 14
Both horizontal-bed and axial columns are Vacuum pump power (kW) 80 80 74 78
commonly manufactured and exhibit Vacuum pump capacity (scfm) 13,000 13,000 13,000 13,000
good flow distribution. Axial-flow col- Total capital investment ($) 3,099,000 2,450,000 1,408,000 1,230,000
umns would be applicable for smaller air Adsorption subsystem costa 36% 45% 34% 39%
flow systems (<20,000 cfm) because they Adsorbent inventory cost 43% 20% 32% 14%
are easier to fabricate and implement. Ra- Microwave subsystem costsb 13% 24% 15% 29%
c
dial-flow columns are less common and Recovery subsystem costs 7% 10% 16% 19%
d
suffer from flow maldistribution problems. Total operating costs ($/yr) 462,000 639,000 238,000 331,000
Levelized cost, COS ($/lbm) 0.206 0.221 0.099 0.113
In addition to adequate heating, effi-
cient desorption requires that the VOCs a
Includes the cost of the vessels, instrumentation, fans, recovery tank, condenser, decanter, and internal piping.
be quickly removed from the gas space in
Does not include adsorbent inventory.
the bed. It was found that microwave re- b Includes cost of microwave generator, power measurement and control, applicator, and waveguides.
generation of fixed beds favors vacuum c Includes cost of the vacuum pump (condenser and other costs are included with adsorption system costs).
purge rather than flowing an inert stream d Includes cost of cooling water, electricity, microwave power tube replacement, adsorbent replacement, mainte-
through the bed because of lower micro- nance, overhead, property taxes, and insurance.
wave and refrigeration costs. For vacuum-
purge systems, a regeneration pressure of about 5 torr pro- Environmental Solutions Program. Adsorbent samples and
vides the optimal balance between the cost of the micro- technical information were provided by Dow Chemical
wave and vacuum equipment. Either a dry vacuum pump Company and UOP Molecular Sieves. The authors would
or a refrigerated condenser may be employed as the like to thank Dr. H. Robert Goltz of Dow Chemical for
vacuum source. In contrast with conventional regenera- reviewing a draft of this paper.
tion systems, the adsorbent bed should be regenerated to
near-zero coverage. NOMENCLATURE
COS Levelized cost per pound of
ACKNOWLEDGEMENTS treated solvent [$/lbm]
This project has been funded in part with Funds from the LMTZ Length of the mass transfer zone [m]
U.S. Environmental Protection Agency (EPA) as part of PPM Parts per million gas concentration [—]
the program of the Gulf Coast Hazardous Substance Re- q Sorption coverage [wt. %]
search Center. The contents do not necessarily reflect the T Temperature [°C]
views and policies of the EPA nor does the mention of v Velocity [m/s]
trade names or commercial product constitute endorse- δ Depth of microwave penetration [m]
ment or recommendation for use. Additional grants were ε’ Dielectric constant [—]
provided by Borden, Inc., and the University of Texas

1144 Journal of the Air & Waste Management Association Volume 48 December 1998

ε” Dielectric loss factor [—]
λ0 Wavelength of microwave radiation
in free space [m]
REFERENCES
1. Burkholder, H.R.; Fanslow, G.E.; Bluhm, D.D. “Recovery of ethanol
from a molecular sieve by using dielectric heating,” Ind. Eng. Chem.
Fund. 1986, 25, 414-416.
2. Singh, V.P. Microwave Regeneration of Molecular Sieves. Canadian Fu-
sion Fuels Technology 1984; Report No. F84023.
3. Roussy, G.; Zoulalian, A.; Charreyre, M.; Thiebaut, J.M. “How micro-
waves dehydrate zeolites,” J. Phys. Chem. 1984, 88, 5702-8.
4. Gibson, C.; Matthews, I.; Samuel, A. “Microwave enhanced diffusion
in polymeric materials,” Microwave Power and Electromagnetic Energy
1988, 23 (1), 17-28.
5. Weissenberger, A.P.; Schmidt, P.S. Microwave Regeneration of
Adsorbents. In Proceedings of Fourth Biennial Symposium on Microwave
Processing of Materials; Materials Research Society: San Francisco, April
1994.
6. Price, D.W.; Schmidt, P.S. “Microwave Regeneration of Adsorbents at
Low Pressure: Experimental Kinetics Studies,” J. Microwave Power and
Electromagnetic Energy 1997, 32 (3), 145-154.
7. Michaels, A.S. “Simplified Method of Interpreting Kinetic Data in
Fixed-Bed Ion Exchange,” Ind. Eng. Chem. 1952, 44 (8), 1922.
8. Price, D.W. Recovery of Volatile Organic Compounds by Microwave
Regeneration of Adsorbents, Ph.D. Dissertation, University of Texas
at Austin, 1996.
9. Price, D.W.; Schmidt, P.S. Design Analysis of Microwave-Regenerated
Adsorbent Systems for Recovery of Volatile Organic Compounds. In
Proceedings of the Microwave and High-Frequency Heating Conference,
Cambridge, UK, September 1995; pp. C4.1-4.
10. Sanio, M.R.; Schmidt, P.S. Cost Estimation for Industrial Dielectric Heat-
ing Systems, Process Energetics Program Report 89-01, Center for En-
ergy Studies, Univeristy of Texas at Austin. 1989.
11. Goltz, H.R. Dow Chemical, Liquid Separation Systems, personal com-
munication, 1994-96.
12. Goltz, H.R.; Jones, K.; Tegen, M. High Surface Area Polymeric
Adsorbents for VOC Capture and On-Site Regeneration. Presented at
the Air & Waste Management Association 87th Annual Meeting &
Exhibition, Cincinnati, OH, June 19-24, 1994, 94-TA42.04.
13. Southworth, J. UOP Molecular Sieves, personal communications,
1993-1995.
14. UOP “Molsiv™ High Silica Zeolites: Product Information,” Des Plaines,
IL, 1993.
15. Xtrusorb™ 600 and 700 Pelletized Activated Carbons. Calgon Car-
bon Corporation, Technical Bulletin, 1993.
16. Davison Molecular Sieves Adsorption Equilibria. Davison Chemical
Division, W.R. Grace & Co., Technical Bulletin, 1994.
Volume 48 December 1998
Price and Schmidt
17. U.S. Environmental Protection Agency. Handbook: Control Technolo-
gies for Hazardous Air Pollutants, June 1991, EPA/625/6-91/014.
18. Vatavuk, W.M. Estimating Costs of Air Pollution Control; Lewis Publish-
ers/CRC Press: Chelsea, MI, 1990.
19. Roy, P.; Schmidt, P.S. Dielectric Loss Factors of Industrial Adsorbents
Loaded with Volatile Organic Compounds. In Proceedings of the 30th
International Microwave Symposium; International Microwave Power
Institute: Denver, CO, July, 1995.
20. Metaxas, A.C.; Meredith, R.J. Industrial Microwave Heating; Peter
Peregrinus: London, 1983.
21. Ruthven, D.M. Principles of Adsorption and Adsorption Processes; John
Wiley & Sons: New York, 1984.
22. Genkin, V.S.; Dil’man, V.V.; Sergeev, S.P. “The Distribution of a Gas
Stream Over the Height of a Catalyst Bed in a Radial Contact Appara-
tus,” Int. Chem. Eng. 1973, 13, 24-28.
23. Ponzi, P.R.; Kaye, L.A. “Effect of Flow Maldistribution on Conversion
and Selectivity in Radial Flow Fixed-Bed Reactors, AIChE J. 1979, 25,
100-108.
24. Chang, H.S.; Calo, J.M. “Design Criterion for Radial flow Fixed-Bed
Reactors, AIChE J. 1983, 29, 1039-1041.
25. Kovach, J.L. Gas-Phase Adsorption. In Handbook of Separation Tech-
niques for Chemical Engineers; Schweitzer, P.A. Ed.; McGraw-Hill: New
York, 1979, p. 3-39.
About the Authors
Dr. David W. Price is a post-doctoral research associate and
Dr. Philip S. Schmidt (corresponding author) is the Donald J.
Douglass Professor of Engineering and Head of the Pro-
cess Energetics Program at the University of Texas at Aus-
tin, Center for Energy and Environmental Resources, Aus-
tin, TX 78712. Dr. Schmidt is the author of two books and
numerous journal articles on industrial thermal process de-
sign and dielectric heating of materials.
Journal of the Air & Waste Management Association 1145