&EPA
                             United States
                             Environmental Protection
                             Agency
EPA/540/SR-95/526
August 1995
                            SUPERFUND INNOVATIVE
                            TECHNOLOGY EVALUATION
                             Emerging  Technology
                             Summary

                             Development of a  Photothermal
                             Detoxification  Unit
                              There has long been interest in uti-
                             lizing photochemical methods for de-
                             stroying hazardous organic materials.
                             Unfortunately, the direct application of
                             classic, low temperature photochemi-
                             cal processes  to  hazardous waste
                             detoxification is often too slow to be
                             practical for wide spread use. Further-
                             more, low-temperature photochemical
                             processes often fail to completely con-
                             vert the targeted  wastes to mineral
                             products which  are either harmless to
                             the environment or easily scrubbed
                             from the system effluent. Researchers
                             at the  University of Dayton Research
                             Institute (UDRI) have developed  a
                             unique photothermal process that over-
                             comes many of problems. Specifically,
                             it has been found that there are numer-
                             ous advantages to  conducting photo-
                             chemical detoxification at relatively high
                             temperatures. Under the conditions of
                             simultaneous exposure to heat and ul-
                             traviolet (UV) radiation the rate of de-
                             structive photothermal reactions can be
                             greatly increased with  complete miner-
                             alization of the waste feed. Furthermore,
                             it has  been demonstrated that at the
                             elevated temperatures  used in this pro-
                             cess the efficiency of  UV radiation ab-
                             sorption also increases resulting in an
                             overall improvement  in process effi-
ciency. These features (i.e., fast, effi-
cient, and complete destruction of or-
ganic wastes) make this a promising
technique for destroying hazardous or-
ganic wastes in the gas-phase. The au-
thors present the theoretical foundation
for the photothermal detoxification pro-
cess along with a summary of the re-
sults from a bench-scale flow reactor
system. The basic design, capital cost,
and  operating cost for a full-scale flow
reactor system using currently avail-
able industrial illumination equipment
is also presented.
  This Project Summary was developed
by the EPA's National  Risk  Manage-
ment Research Laboratory, Cincinnati,
OH,  to announce  key findings  of the
SITE Emerging Technology that is fully
documented in a separate report of the
same title (see Project Report ordering
information at back).

Introduction
  One approach to  destroying hazardous
organic wastes which has received con-
siderable  attention  over the years is the
use of photochemical reactions in place of
conventional thermochemical or combus-
tion  reactions. Photochemical techniques
have been of interest because photochem-
istry, the use of light to induce a chemical

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reaction,  can be  conducted at  relatively
low temperatures, often at  or near room
temperature. Unfortunately, most attempts
to exploit photochemistry as a waste de-
struction technology have been frustrated
by slow reaction rates and the inability to
completely convert waste materials to min-
eral products. Specifically, conducting pho-
tochemistry  at  low temperatures often
requires exposure times of minutes, hours,
and even days to achieve meaningful lev-
els of conversion. Furthermore, the prod-
ucts of the reactions are often other organic
compounds rather than inorganic mineral
compounds such as carbon dioxide,  wa-
                    Side View
ter, and hydrogen chloride. The University
of Dayton Research Institute (UDRI) has
developed a novel photochemical process,
embodied  in  a  device  called  a
Photothermal  Detoxification  Unit (PDU),
which overcomes these problems and of-
fers an efficient means of destroying haz-
ardous organic materials.
  The  PDU, illustrated in  Figure 1, is a
relatively simple  device consisting  of a
thermally insulated vessel enclosing a set
of large, medium-pressure, mercury vapor
lamps.  The  purpose of the lamps is  to
provide an efficient source of near-UV ra-
diation  as well as heat for the process.
Additional heat may  be  provided by unit
operations upstream of the PDU, such  as
a thermal desorption  unit, combustor, a
dedicated preheater,  or other operations.
The  basis for the PDU's operation is  to
use the near-UV radiation from the mer-
cury vapor lamps  to  induce destructive
photochemical reactions  and to conduct
these reactions at moderate temperatures
(i.e., 200-600°C) so they proceed to com-
plete mineralization quickly and efficiently.
Since this process  requires both light,  as
with conventional photochemical  pro-
cesses, and  heat,  it  is  referred to as a
photothermal  detoxification process. The
                    Top View
                                          General Layout of a Four Chamber PDU
                                      Side View                              Top View

                                                     Chamber Details

 Figure 1. Conceptual schematic of a prototype Photothermal Detoxification Unit (PDU) based on a mercury arc lamp illumination system.


                                                             2

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result is a technology capable of destroy-
ing organic materials at temperatures much
lower than thermal processing alone and
at temperatures easily achievable through
non-combustion means. Indeed, the tem-
perature requirements for the system may
already exist for many processes such as
the  thermal  desorption of  contaminants
from soils.

Procedure
  The specific exposure conditions of time,
temperature, and  radiant intensity will be
largely dependent on the  materials  of in-
terest and the required level of destruc-
tion.  In general, these aspects of the PDU
design and operation are brought together
through a reactor performance model such
as
                                (1)
  where fr is the fraction remaining in the
process stream exiting the PDU,  kgnd is
the rate of thermal reactions,  kab is the
rate of light absorption,  $ is an efficiency
term for  the  photothermal  reactions re-
ferred to as the quantum yield, and t is
the mean exposure time. In  the PDU, the
rate of thermal  reactions should be rela-
tively small, but it is important to explicitly
include it for those cases where the  sys-
tem may be operated at higher tempera-
tures and thermal reactions can become
important. The rate of light absorption re-
flects the extent of overlap  between the
emission spectrum of the light source and
the absorption spectrum of the waste. This
term is also dependent on the intensity of
the light source and  the number of lamps
used. The quantum  yield is an efficiency
term describing what fraction of the light
absorbed actually results in destruction of
the waste feed.  Finally, the mean expo-
sure  time reflects the size of the PDU and
the rate of flow through the  system. Note
that all of these terms lie in  the exponent
of Equation  1  and therefore can have a
powerful  influence on the performance of
the PDU.
  Other reactor performance models may
be used to describe the PDU, but all share
the same basic features  of Equation  1.
Specifically, to predict the performance of
the PDU, and hence define a system for a
given application, it  is necessary to have
knowledge of the thermal chemistry (k d),
the photochemistry (c|>), and the UV ab-
sorption behavior (kab) of the system. Fur-
thermore, all of these aspects of the PDU
are expected to be functions of tempera-
ture.  Unfortunately, since the PDU  oper-
ates  under unique circumstances, none of
the required high-temperature  spectro-
scopic and photochemical  data is  avail-
able  from  the literature.  Therefore,
researchers at UDRI designed and built a
High Temperature Absorption Spectropho-
tometer (HTAS)  to obtain the necessary
spectroscopic  data, and  a Laboratory
Scale-Photothermal  Detoxification  Unit
(LS-PDU) for  the  basic  thermal  and
photothermal information.  The latter was
particularly useful for demonstrating the
effectiveness of the photothermal process.
  The  HTAS,  shown in  Figure  2, is a
custom built, single-beam spectrophotom-
eter capable of operating at temperatures
as high as  1,000°C.  Since  the  organic
molecules for  which  the  HTAS was de-
signed to  study tend to  decompose with
prolonged exposures at elevated tempera-
tures, the  system is fitted with a flow cell
rather than  a  static  cell found in most
commercial spectrophotometers. Further-
more, an inert carrier gas (i.e., nitrogen) is
used for sample transport to eliminate the
possibility of sample oxidation. By flowing
a carrier gas  laden  with the sample  of
interest through the cell the length of ex-
posure to elevated temperatures can be
kept short (typically 1  sec) to limit destruc-
tion of the sample at very high tempera-
tures.
  The LS-PDU,  shown in Figure 3, is a
dedicated  flow reactor system capable  of
obtaining thermal and photothermal de-
composition  data on  a  great  variety  of
compounds.  Structurally, the  LS-PDU
shares many features with the HTAS. For
example,  the  LS-PDU  includes dual
sample  inlets  connected  to  a  cylindrical
vessel through a single  sample  transfer
line.  However, whereas  the HTAS was
design to  prevent reactions  from taking
place in  the system, the LS-PDU was
designed to conduct reactions under care-
fully  defined conditions and  analyze the
products of those reactions. For this pur-
pose the vessel connected to the inlet line
                                            OMA
                                                          Absorpbon
                                    Focussing
                                      Optics
                                                 Furnace
                                             \
                                      1
                       OMA
                         Morsochrometar    Vent

                                                       Sampte Inlets
                                           Deuterium
                                              Lamp
                                                                            ;
Figure 2. General schematic of the High Temperature Absorption Spectrophotometer (HTAS) showing the principal elements of this system.

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                                 Workstation
                             X
                                                                   HFID Workstations
                                                                                           Xenon Arc
                                                                                           Lamp
                                                                                        Intel Heaters
                                                                         Sample Inteis
Figure 3. General schematic of the Laboratory Scale-Photothermal Detoxification Unit (LS-PDU) showing the principal elements of this system.
\s  a small  cylindrical  reactor measuring
1.2 cm in diameter by 8.4 cm long. The
exhaust from the reactor flows through a
heated transfer line to a trapping system
which collects all of the condensable ma-
terials from the flowing gas. This trap is a
single tube-in-shell design similar to a labo-
ratory condenser. The  shell side is cooled
with nitrogen gas which has  in turn been
cooled by a liquid  nitrogen bath.  This al-
lows the  trap to operate at temperatures
as low as -180°C,  though -160°C is rou-
tinely used.  During the effluent collection
phase of operation the exhaust from the
trap is vented to a fume hood. In prepara-
tion to analyze the  collected material, this
vent is closed which  directs the flow  of
gas to an inline analytical system  consist-
ing of a programmed temperature, capil-
lary column gas chromatograph (GC) fitted
with dual  columns  and  an inlet  splitter.
One of the  columns  is connected to a
scanning quadrapole mass spectrometer
(MS), the other to  a hydrogen  flame ion-
ization detector (FID).  The LS-PDU may
be  operated at temperatures  as  high as
1,000°C  and used with nearly any UV
radiation  source. It is currently configured
with a  pulsed dye  laser, solar simulator,
and a high pressure xenon arc lamp.
  All samples used in the tests described
below were high  purity standards (typi-
cally 99+%) obtained from commercial sup-
pliers.
Results and Discussion
  Conducting photochemical detoxification
at elevated  temperatures improves  the
overall efficiency of the  process in three
important areas; the spectroscopy, the rate
of destruction, and the  completeness of
the destruction.
  The impact of temperature on the spec-
troscopy is  illustrated by the high tem-
perature    absorption   spectra   for
trichloroethylene (TCE)  shown in  Figure
4. For comparison, the emission spectra
for  high-pressure, xenon arc (which was
used  on the LS-PDU) and medium-pres-
sure,  mercury vapor lamp (proposed for
the PDU) are shown in Figure 5. The data
summarized  in Figure 4  show that as the
temperature  increases,  the  absorption
spectrum shifts to longer wavelengths and
increases  in  overall intensity. The  net re-
sult is that the overlap between the emis-
sion spectrum of the light source and the
absorption spectrum of the sample in-
creases with temperature. In the case of
TCE,  the  rate of photon absorption with
xenon arc as the  radiation source,  in-
creases over  8-fold  as  the temperature
increases  from 100 to 600°C. Recalling
that the reactor performance model sug-
gests  an exponential dependence  on  the
rate of absorption, this is a very significant
feature of the photothermal process.
  The most  important  aspect  of the
photothermal process is  whether the light
absorbed by the waste feed results in the
destruction of the  waste feed.  The  LS-
PDU data for TCE exposed to 18.1 W/cm2
of xenon arc radiation  for 10 sec in air
(summarized in  Figure  6) show  that is
indeed what happens.  Specifically, this
example  clearly shows the photothermal
process is capable of destroying a signifi-
cant portion of the TCE  under conditions
where no thermal destruction is occurring.
For example, at 500°C  the thermal  de-
composition has not yet  begun, while the
photothermal process  has destroyed  ap-
proximately 60% of the sample.
  The data presented in  Figure 6 seem to
suggest that the thermal and photothermal
processes become equally efficient at high
temperatures (i.e., above 600°C).  How-
ever, this is in fact an artifact  of how the
data is presented. If we compare the ratio
of the fraction remaining undestroyed from
a thermal exposure to the fraction remain-
ing from a photothermal exposure (a value
referred to as the photothermal enhance-
ment ratio), we find the photothermal pro-
cess actually continues  to improve over
the comparable thermal  process through-
out the temperature range (cf.  Figure 7).
  The  results for TCE illustrate  that it is
important to utilize a reactor  model that
explicitly  includes the thermal component
of the  photothermal process so that the
two components may be separated in the
course of interpreting data from the bench-

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                                     2,500-
                                     2,000-
                                     1,500-
                                £    1,000-
                                      500-
                                         0
                                                 	600°C
                                                 	500°C
                                                 	 400°C
                                                 	300°C
                                                 	  - 200°C
                                               1 '  I ' '  ' ' I '  ' ' ' I  ' ' ' T-I • i  i i |  • i • i  | • i  • i | i  i i
                                          230   240    250   260   270    280   290    300   310
                                                              Wavelength, nm

Figure 4. The absorption spectra for trichloroethylene at 100, 200, 300, 400, 500, and 600'C showing that the absorption shifts to longer wavelengths and
         increases in intensity as the temperature increases.
8
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                                                                                                   2.
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                                        220   230   240   250   260   270  280  290   300
                                                            Wavelength, nm

Figures. The spectral radiance of IW/cm2 of medium pressure mercury and high pressure xenon arc emission showing the xenon arc spectrum
         (approximately 2.5% of which is at wavelengths less than 300 nm) is spread out as broad-band emission, while the mercury arc spectrum (of which
         approximately 15% is at wavelengths less than 300 nm) is concentrated in narrow emission lines.
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            5.0-
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      CL
4.5-

4.0-

3.5-

3.0-

2.5-

2.0-

1.5-

1.0
               200     300     400     500     600
                                  Temperature,°C
                                                      700
                                                              800
Figure 7. The ratio  of the fraction remaining following thermal and photothermal exposures for
        trichloroethylene exposed to 0 (thermal) and 18.1  W/cm2 (photothermal) of xenon arc
        radiation for 10 sec in air showing that the photothermal process steadily increases in
        efficiency compared to the thermal process as the temperature increases.
scale system. In  this way,  fundamental
information can be obtained to predict the
performance  of full-scale  systems.  Al-
though the results for TCE  demonstrate
that the exposure conditions used in  the
bench-scale system are probably inappro-
priate for a full-scale system, the data are
still valuable for the fundamental informa-
tion contained. The thermal data yield in-
formation about the thermal decomposition
needed for the PDU model, and  the spec-
troscopy  (ca.  Figures 4 and  5)  gives  the
light absorption rate information. When this
information  is  combined with  the
photothermal  destruction data,  the quan-
tum yield  can be  extracted as  shown in
Figure 8. These results illustrate that the
rate  of destructive photochemical  reac-
tions  is increasing with temperature (the
decrease  in quantum yield  between 550
and 600°C is thought to result from com-
peting thermal  reactions which become
significant in this temperature region). Re-
calling that the  rate of photon absorption
also  increases with temperature, the data
clearly show the importance  of high tem-
perature in the photothermal  process.
  The last  important aspect of the
photothermal  process is its ability to com-
pletely mineralize the waste feed (i.e., con-
vert  to mineral  products  of  complete
conversion such as carbon dioxide, water,
hydrogen  chloride,  etc.).  The  data  for
1,2,3,4-tetrachlorodibenzo-p-dioxin (TCDD)
shown in  Figure 9 demonstrate that  the
photothermal  process can easily destroy
this type of hazardous material which has
traditionally challenged conventional waste
                             destruction techniques. The efficiency of
                             the photothermal process is clearly shown
                             in the enhancement  ratio  data  summa-
                             rized  in Figure 10. As  in the case of TCE,
                             the photothermal enhancement increases
                             throughout the temperature range and by
                             600°C it reaches a value of nearly  1,300.
                             In addition to demonstrating the high  effi-
                             ciency in  destroying TCDD, this  data set
                             allows  direct  observation  of how  a
                             photothermal reactor behaves when oper-
                             ating  in a predominantly  photo mode (as
                             compared  to a combined  photo/thermal
                             mode as in the case of the LS-PDU data
                             for TCE).  It is instructional to examine the
                             chromatograms from these tests.
                                LS-PDU GC/FID traces  from thermal
                             exposures at 300°C (100% remaining) and
                             600°C   (35.4%   remaining),  and  a
                             photothermal exposure at600°C (0.0285%
                             remaining) for TCDD  are summarized in
                             Figure 11. The 600°C thermal data illus-
                             trate  the  production  of  numerous PICs
                             that often accompany  the thermal decom-
                             position  of organic  compounds. The
                             photothermal trace clearly shows that not
                             only is the parent TCDD  destroyed  under
                             these conditions, but nearly all of the as-
                             sociated products  as well. Furthermore,
                             the data shown here  include  all products
                             that were condensable at  -160°C (the tem-
                             perature at which  the LS-PDU's effluent
                             trap was operated),  so  that all but the
                             lightest organic products (such  as  meth-
                             ane and ethane) are recovered. This  em-
                             phasizes  that the  photothermal  process
                             differs significantly from  conventional di-
                             rect  photochemical  processes in that
photothermal decomposition reactions lead
to the complete mineralization of the waste
feed.
  With  the available laboratory-  and
bench-scale reactor data,  it is now  pos-
sible to  predict the performance of a full-
scale PDU, given the geometry  of  the
reactor  and the  emission  characteristics
of the illumination system.  In the PDU in
Figure 1, the basic reactor vessel is shown
as a cylinder measuring 2.5 m  (8.2 ft) tall
and 2m  (6.6 ft) in diameter  giving an inter-
nal volume of 7.85 m3 (277 ft3).  The illumi-
nation system  consists of  six medium
pressure mercury lamps delivering 15 kW
of radiant energy each with a nominal arc
length of 2 m (6.6 ft).  This gives a mean
radiant intensity of 1.23 W/cm2 with a near-
UV spectral distribution (cf.  Figure 5). Per-
formance    estimation    using    a
tanks-in-series model suggests that a com-
plete  PDU  system should  consist  of four
such vessels connected in series. In this
arrangement the  system performance
would approach that of a plug  flow reac-
tor, which would offer the highest theoreti-
cal  destruction efficiency.  Therefore,  the
PDU system would  have an internal vol-
ume of  31.4 m3,  or approximately 1,100
ft3.  Larger  capacity can be achieved  by
operating  additional chambers in  series,
or sets of chambers in parallel.
  The performance of a four-chamber
PDU expressed in terms of the estimated
capacity achieving 99% destruction in ac-
tual fP/min for selected compounds is sum-
marized in Table 1. These  results indicate
that  for  volatile organic compounds,  the
PDU should be operated at temperatures
greater  than 500°C and throughputs  on
the  order of 1,000-3,000 cfm can  be ex-
pected. The performance for semi-volatiles
may be  much  greater,  both in  the allow-
able temperature range  (greater than
300°C) and capacity (2,000 to 6,000 cfm).
This illustrates  that the  PDU is  capable of
processing VOCs  at  high temperatures
and  is  particularly well suited for semi-
volatile compounds where  it can be oper-
ated at  lower temperatures. Furthermore,
there are other types of lamps which may
be used (i.e., low pressure mercury,  xe-
non excimer, etc.) which could give better
performance for volatile compounds.
  The overall capital and operating costs
for the PDU chamber illustrated in Figure
1 were calculated as summarized in Table
2. In this table  the costs for the shell and
insulating firebrick where taken  to be simi-
lar to that reported for a hazardous waste
incinerator  afterburner and corrected  to
1995 costs. The cost for the lamps, lamp
wells, and lamp ballasts were taken from
the  manufacturer's literature. These  esti-

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                                  0.6
                           a
                                  0.3-
                                  0.2-
                                  0.1
                                                       I '  '  ' '  I
                                     200     300     400     500     600
                                                        Temperature, °C
                                             700
                                                      800
Figure 8.  The photothermalquantum yieldfortrichloroethylene illustrating the rate of'the photochemical reactions increasing with temperature. The observed
         increase in the overall efficiency of the photothermal process is a result of this increase in the reaction rate and the increase in the efficiency of near-
         UV light absorption.
                                     100-
                                                                       —•— Thermal
                                                                       - -e - - Photothermal
                                      40-
                                        200     300     400     500     600
                                                            Temperature, °C
                                                                                  700
                                                                                          800
Figure 9.  Conversion as a function of temperature for 1,2,3,4-tetrachlorodibenzo-p-dioxin exposed to 0 (thermal) and 18.1 W/cm2 (photothermal) of xenon
         arc radiation for 10 sec in air showing that the photothermal process can destroy this compound to very high levels at relatively low temperatures.
                                 1400-
                            o

                            D^


                            "ro

                            0

                            t
1200-


1000-


 800-j


 600-


 400-


 200-


   0
                                     200
                                             300
                                                      400     500     600
                                                         Temperture, °C
                                                                              700
                                                                                       800
                                                             Temperature, °C

Figure 10.  The ratio of the fraction remaining following thermal ana pnowmermai exposures ror i,^,3,4-tetrachlorodibenzo-p-dioxin exposed to 0 (thermal)
           and 18.1 W/cm2 (photothermal) of xenon arc radiation for 10 sec in air showing that the photothermal process steadily increases in efficiency
           compared to the thermal process as the temperature increases.

                                                                   7

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                                      300°C, thermal (no conversion)
                                                                         TCDD
                           o
                           Q.
                           U)
                           &
                           g
                           LL
                           O
                           O
                                        600°C, thermal
                                                        Organic PICs
                                                                           TCDD

                                     600°C, 17.6 W/cm    xenon arc radiation
                                           5       10       15      20       25      30
                                         Chromatographic Retention Time, min.
Figure 11. Example GC/FIDchromatograms from TCDD exposedto 300 thermal, 600 thermal, and600°C photothermal (17.6 W/cm2) for 10 sec in air showing
          that the photothermal process destroys the complex mixture of PICs (or prevents their formation) as well as the parent compound.

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Table 1. Estimated PDU1 Capacity2 for Selected Compounds
    Compound
              Temperature ('C)
                                         300
                                                     400
                                                                500
                                                                            600
Trichloroethylene
m-Xylene
Chlorobenzene
1,2,3,4-Tetrachlorodibenzo-p-dioxin
131
53
98
2,190
384
60
131
2,504
937
158
427
3,300
2,590
1,900
1,730
5,780
1 Four 2.5x2 m chambers fitted with six 15 kWmedium pressure mercury lamps.
2 Expressed as actual cubic feet per minute achieving 99% destruction.
Table 2. Estimated Costs for a Single PDU Chamber Fitted with Six 15 kW Medium Pressure
        Mercury Lamps
    Item
                           Cost
                                            Expected Life
                                                                  Annual Cost
Carbon Steel Shell
Firebrick Insulation
Lamp Wells
Lamp Ballasts
Support Structure
Sub Total
Lamps
Sub Total
Electrical Service7
Grand Total
Hourly Cost3
$20,800 1
$1,3702
$8,400
$8,500
$8,500 5
$47,570
$3,000
$50,570

20 years
5 years
2 years3
4 years4
20 years
6 months8

$1,040
$274
$4,200
$2,125
$425
$8,064
$6,000
$14,064
$22,500
$36,564
$7.31
1 Assuming $86/ft2
2 Assuming $1.44/ft2-in.
3Assuming 10,000 hr life and 5,000 hr of operation/yr.
4 Assuming 20,000 hr life and 5,000 hr of operation/yr.
5 Assuming support structure and equipment is 20% of the chamber cost less support.
6 Assuming 2,500 hr life and 5,000 hr of operation/yr.
1 Assuming $0.05/kW-hr and 5,000 hr of operation/yr.
sAssuming 5,000 hr of operation/yr.
mates suggest the majority of the capital
costs will be in fabricating the reactor shell,
followed  by the lamp wells, ballasts, and
the system  support structure and equip-
ment.
  With respect to the amortized costs (us-
ing a simple linear depreciation model),
Table 2 suggests the most expensive com-
ponent will  be the  lamps and the  lamp
wells. The 2,500 hr used for the lamp life
was based on the manufactuer's estimate
assuming 5 hr of operation for every lamp
start. Discussions with lamp manufactur-
ers indicate that since the lamps will likely
see continuous service  in the PDU, sig-
nificantly longer service  life is likely. This
should reduce overall cost of the lamps
and, hence,  the  operating costs  of the
PDU.  The second highest amortized cost
is the lamp wells which are expected to
degrade from attack from dust and water
vapor.  The cost  estimates  assume the
lamp wells  are replaced with new wells for
every 10,000 hr of operation. If the wells
can be  replaced  with  refurbished  units,
this cost could be reduced.
  With respect to consumable materials
only electricity for the lamps is considered
here.  As Table 2 illustrates, electricity is
the largest single contributor to the overall
cost of the PDU. The relatively high elec-
trical energy requirement comes from the
fact that only about 15% of the electrical
energy is converted to useful near-UV ra-
diation.  If other lamps are made available,
such as low  pressure mercury or  xenon
excimer, this  cost  could  be considerably
reduced by the thermal contribution to the
system  from the lamps. Specifically, in a
well insulated  vessel the 90 kW supplied
to the chamber by the six 15 kW lamps is
sufficient to  heat approximately 600 cfm
of air saturated with water vapor (as from
a soil vapor extraction unit) from 15°C to
500°C. Therefore, depending on the spe-
cific site requirements,  the heat from the
lamps  should reduce  the  size  of a
preheater, or even  eliminate one entirely.
The estimate  summarized in Table 2 sug-
gests the overall operating cost for a PDU
based on the  design presented in  Figure
1 should be approximately $8/hr-chamber
including the  depreciation  of the  equip-
ment,  replacement lamps, and required
electrical service.

Conclusions and
Recommendations
   In summary, the photothermal detoxifi-
cation  process offers  a  technologically
simple and effective means of destroying
organic materials  in gaseous process
streams. It  is a non-combustion process,
so additional  fuel and gases  (e.g.,  com-
bustion  air)  are  not required,  though  in
some cases  (e.g.,  low temperature pro-
cesses  such  as  soil vapor extraction) a
preheater  may be  needed. Furthermore,
the process efficiency  is  not  dependent
on initial concentration  making it  ideally
suited for dilute  waste streams. Results
from bench-scale tests show that the pro-
cess is  exceptionally efficient in destroy-
ing semi-volatile  wastes  such  as  dioxins
which suggests similar results may  be ex-
pected  for  related  compounds such  as
polychlorinated     biphenyls    and
dibenzofurans. Estimated capital and op-
erating  costs  suggest  the photothermal
process should be relatively economical
to implement  using currently available in-
dustrial illumination  systems and hardware,
and that future advances in near-UV illu-
mination systems should reduce the over-
all cost even further. Given these results it
is recommended  that  the PDU be ad-
vanced  to the level of a  pilot-scale dem-
onstration at an appropriate Superfund site.

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 John L. Graham, Barry Dellinger, and Joseph Swartzbaugh are with Environmen-
   tal Science and Engineering Group, University of Dayton Research Institute,
   Dayton, OH 45469-0132.
 Chien T. Chen is the EPA Project Officer (see below).
 The complete report, entitled "Development of a Photothermal Detoxification
     Unit," (Order No. PB95-255733; Cost: $27.00, subject to change) will be
     available only from:
         National Technical Information Service
         5285 Port Royal Road
         Springfield, VA 22161
         Telephone: 703-487-4650
 The EPA Project Officer can be contacted at
         National Risk Management Research Laboratory
         U.S. Environmental Protection Agency
         Edison, NJ 08837
United States
Environmental Protection Agency
National Risk Management Research Laboratory (G-72)
Cincinnati, OH 45268

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