Note: Descriptions are shown in the official language in which they were submitted.
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TITLE OF THE INVENTION
CARBON-BASED ADSORPTION POWDER CONTAINING CUPRIC CHLORIDE
BACKGROUND OF THE INVENTION
The present invention relates to an adsorption powder useful for the
removal of metal and organic pollutants from gas streams. The adsorption
powder is
typically useful for treating solid waste contaminates, e.g. contaminated soil
treatment
by high efficiency incineration. More particularly, the invention relates to
the capture
of mercury and other metals, dioxins, furans and other organic compounds from
high
1o temperature, high moisture gas streams using an adsorption powder
containing cupric
chloride.
Strict standards exist for particulate and total mercury emissions by
coal-fired power plants, petroleum refineries, chemical refineries, coal fired
furnaces,
trash burning facilities, incinerators, metallurgical operations, thermal
treatment units
15 and other particulate and mercury emitting facilities. These same
restrictions apply to
mercury vapor, which can enter the atmosphere as a result of low temperature
thermal
desorption (LTTD) treatment of contaminated soils.
These stringent standards exist in order to protect the environment and
the community. When mercury-containing gases are released, the gases disperse
and
2o mercury is deposited over a wide area. The dispersed mercury can accumulate
in the
soil or water supplies, where it may be incorporated into the food chain.
Mercury
is extremely harmful to aquatic life and ultimately to the humans who consume
mercury-contaminated plants and animals. It is necessary, therefore, to have a
safe
and effective method of eliminating mercury from~the environment.
25 The problem of the capture and treatment of mercury vapor, typically
in the context of coal-fired power plants and waste incinerators, has been
previously
considered. For example, U.S. Patent No. 3,193, 987 discloses passing mercury-
containing vapor over activated carbon impregnated with a metal which forms an
amalgam with mercury. U.S. Patent No. 4,094,777 discloses passing a mercury-
3o containing vapor over an adsorption .mass consisting essentially of a
support, sulfided
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copper and sulfided silver. U.S. Patent No. 3,876,393 discloses passing
mercury-
containing vapors over activated carbon that has been impregnated with
sulfuric acid.
Selenium has also been used in the removal of mercury from a vapor. U.S.
Patent
No. 3,786,619 discloses passing a mercury-containing gas over a mass
containing
as an active component, selenium, selenium sulfide or other selenium
compounds.
Electrostatic precipitators and various filters have traditionally been used
for mercury
removal, although complex apparatus have also been disclosed. (See e.g., U.S.
Patent
Nos. 5,409,522 and 5,607,496.)
The problem of recapturing mercury from power plant gas streams
to is analogous to the need for recapturing mercury from incinerators that
treat
contaminated soils. A process currently in use at soil treatment facilities is
known as
low temperature thermal desorption (LTTD). LTTD is the main process by which
contaminated soils are treated to remove mercury and other contaminants. In
this
process, contaminated soils are fed into a heating furnace, most commonly a
rotary
15 kiln/drum, where the soil is heated by conduction. The heating volatizes
the soil
components and when a thermal oxidizer is added, the components are oxidized
to
manageable gases, such as CO2, Clz, NOX and SOX, where x is 1-3.
The hot gas stream is subsequently cooled. The stream may be
quenched with water, which cools the stream and concurrently increases the
moisture
2o content. Although water quenching is a highly effective cooling method,
this treat-
ment increases the difficulty of removing mercury from the gas stream. The gas
stream is further treated to reduce and remove metals, HCl, NOX and SOX using
acid
scrubbers, carbon beds, condensation units and through the addition of
adsorption
powders.
25 When adsorption powders are injected into the gas stream, mercury
and other metals bind to moieties present in the powder, precipitating them
from the
gas stream. The powdex-bound mercury is ultimately collected in a bag house
for
appropriate disposal, while the clean gas stream is exhausted to the outside
atmosphere. The problem with standard LTTD methods is that some metals, such
as
3o mercury, are not removed from the stream at high efficiency and will move
with the
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gas stream, ultimately into the environment. Other methods require the use of
complex machinery and expensive adsorption beds. LTTD and other methods also
suffer from the limitation that mercury removal from high moisture gas streams
is
much more difficult than mercury removal from dry streams.
Available adsorption powders remove organics, metals and other
contaminants, but they do not effectively remove mercury. For example, one
available powder (Sorbalita TM) consisting of carbon, calcium hydroxide and
sulfur
removes HCl from a gas stream, but it removed only about 55-65°10 of
the mercury.
Another powder (WUELFRAsorb-C TM) consisting of alcohol saturated lime and
activated carbon is also inefficient at removing mercury.
Some powders include sulfur or iodine impregnated carbon. At
temperatures of 75°C or less, sulfur or iodine impregnated carbon based
powders
show a 95010 mercury removal efficiency, however, powders formulated with
sulfur
impregnated carbon require that the gas stream to which they are added is dry.
Lastly, the mercury removal efficiency of the powders described
and other available powders is known to be very temperature dependent, placing
an additional limitation on powder formulations.
Accordingly, there is a need in the industry for an adsorption powder
that effectively removes metals and other organic compounds, in general, and
mercury, in particular, from high temperature, high moisture gas streams
generated by
the incineration of contaminated soils, treatment of hazardous materials,
combustion
of coal and other mercury liberating sources. The powder must be inexpensive
and
easy to use. Ideally, such an adsorption powder can be employed at treatment
facilities already in place and can take advantage of equipment already in
position,
without requiring retooling or reconfiguring existing equipment.
SUMMARY OF THE INVENTION
There is disclosed an adsorption powder and method for removing
mercury, other metals, and contaminants from a gas stream comprising an
adsorption
powder, wherein the powder is characterized as containing a carbon-based
powder
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selected from the group consisting of coal carbons, wood carbons, graphite
carbons,
activated carbons, coconut shell carbons, peat carbons, petroleum cokes,
synthetic
polymers, the like, and combinations thereof, and an effective amount (about 3
to
about 10 weight percent) of cupric chloride. Optionally, sulfur, potassium
iodide and
permanganate, calcium hydroxide, and combinations thereof may be added to the
powder.
The invention also relates to a process for removing mercury and organic
compounds from gaseous streams using an adsorption powder, characterized as
containing a carbon-based powder selected from the group consisting of coal
carbons,
wood carbons, graphite carbons, activated carbons, coconut shell carbons, peat
carbons, petroleum cokes, synthetic polymers, the like, and combinations
thereof, and
an effective amount (about 3 to about 10 weight percent) of cupric chloride,
the
process being characterized by the steps of:
a) placing a solid phase mercury-containing contaminated soil
feed into a rotary kiln/drum;
b) heating said kiln/drum containing said soil feed to form
gaseous and solid components of the sample;
c) transfernng the gaseous component of said soil feed to an
exhaust cleaning unit/afterburner and the solid component of
2o clean soil to a soil cooling unit;
d) heating the gaseous component of said contaminated soil feed
in said exhaust cleaning unit/afterburner;
.e) cooling the gaseous component of said contaminated soil feed;
f) adding the adsorption powder to the gaseous component;
g) transfernng the powder-containing gaseous component to a
baghouse; and
h) releasing the substantially mercury-free gaseous component of
said sample to the atmosphere.
Optionally, sulfur, potassium iodide and permanganate, calcium
hydroxide, and combinations thereof may be added to the powder.
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BRIEF DESCRIPTION OF THE DRAWINGS
The instant invention will be more fully understood in the following
detailed description, however, the invention is not confined to the precise
disclosure.
Changes and modifications may be made that do not affect the spirit of the
invention,
nor exceed the scope thereof, as expressed in the appended claims.
Accordingly, the
instant invention will now be described with particular reference to the
accompanying
drawings.
Figure 1 is a view in elevation of a schematic diagram illustrating the
to design of an LTTD facility in which the claimed adsorption powder can be
used to
remove mercury from gas streams; vand
Figure 2 is a view in elevation of a schematic diagram illustrating the
bench scale model of the LTTF facility.
15 DETAILED DESCRIPTION OF THE INVENTION
There is disclosed an adsorption powder suitable for removing metals
and organic compounds from high temperature, high moisture gaseous streams,
wherein the metals are selected from the group consisting of mercury, lead,
nickel,
zinc, copper, arsenic, cadmium, other heavy metals, and combinations thereof,
20 wherein the organic compounds selected from the group consisting of furans
and
dioxins. The powder may be characterized as containing a carbon-based powder
and
an effective amount of cupric chloride, i.e. from about 90 to about 97 weight
percent
carbon-based powder and from about 3 to about 10 weight percent of cupric
chloride.
It has been found that the addition of cuprous and cupric chlorides to
25 carbon-based powders provides suitable efficiency for removing metals and
organic
compounds from high temperature, high moisture vaporous streams. While the
addition of other ingredients may enhance metal removal efficiency, dependent
upon
the operating conditions of the removal process, the addition of copper, in
various salt
forms, to a carbon-based powder will aid the efficiency of metals removal from
3o various gas streams.
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Typically, the performance of the carbon-based powder may be further
enhanced, dependent upon the process of removal operating conditions, by the
addition of calcium hydroxide, sulfur, potassium permanganate, potassium
iodide and
combinations thereof, and like compounds.
In one embodiment of the invention, the adsorption powder is
characterized as containing from 0 to about 62 weight percent of calcium
hydroxide,
from 0 to about 4 weight percent of sulfur, from 0 to about 15 weight percent
of
potassium permanganate, from 0 to about 10 weight percent of potassium iodide,
from
about 3 to about 10 weight percent of cupric chloride, and a balancing weight
percent
to of carbon-based powder to provide 100, total, weight percent of adsorption
powder.
Within this embodiment is a powder characterized as containing a carbon-based
powder, calcium hydroxide, potassium iodide, and cupric chloride,
characterized as
containing from about 35 to about 38 weight percent of carbon-based powder,
from
about 52 to about 62 weight percent of calcium hydroxide, from about 5 to
about 10
15 weight percent of potassium iodide, and from about 3 to about 10 weight
percent of
cupric chloride. While another embodiment is a carbon-based, calcium
hydroxide,
potassium permanganate, and cupric chloride powder, characterized as
containing
from about 35 to about 38 weight percent of carbon-based powder, from about 52
to
about 62 weight percent of calcium hydroxide, from about 5 to about 10 weight
2o percent of potassium permanganate, and from about 3 to about 10 weight
percent of
cupric chloride. Still in another variation of this embodiment, the adsorption
powder
may contain from about 35 to about 38 weight percent of carbon, from about 52
to
about 62 weight percent of calcium hydroxide, from 1 to about 4 weight percent
of
sulfur, from about 5 to about 10 weight percent of potassium permanganate, and
from
25 about 3 to about 10 weight percent of cupric chloride.
In yet another embodiment of the invention, the adsorption powder
may be characterized as containing from about 35 to about 38 weight percent of
carbon, from about 52 to about 62 weight percent of calcium hydroxide, from
about 0
to about 4 weight percent of sulfur, and from about 3 to about 10 weight
percent of
3o cupric chloride. In still a further embodiment of the invention, the powder
is
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characterized as containing about 38 weight percent of carbon, about 58 weight
percent of calcium hydroxide, about 4 weight percent of sulfur, and about 4
weight
percent of cupric chloride.
In one embodiment of the invention the potassium permanganate- and
potassium iodide-containing powders, optionally, may be impregnated onto a
carbon
substrate as will become apparent to those skilled in the art. One aspect of
this
embodiment is a powder characterized as containing from about 35 to about 38
weight percent of coal carbon, from about 52 to about 60 weight percent of
calcium
hydroxide, from about 5 to about 10 weight percent of potassium iodide
impregnated
l0 onto a carbon substrate, and from about 5 to about 10 weight percent of
cupric
chloride. However, the identical potassium iodide component may be in blended
with
other components to form the adsorption powder.
The invention is also directed to a process for removing mercury and
organic compounds from gaseous streams using the adsorption powder described
herein, the process being characterized by the steps of:
a) placing a solid phase mercury-containing contaminated soil
feed into a rotary kiln/drum;
b) heating said kiln/drum containing said soil feed to form
gaseous and solid components of the sample;
c) transfernng the gaseous component of said soil feed to an
exhaust cleaning unit/afterburner and the solid component of
clean soil to a soil cooling unit;
.d) heating the gaseous component of said contaminated soil feed
in said exhaust cleaning unit/afterburner;
e) cooling the gaseous component of said contaminated soil feed;
f) adding the adsorption powder to the gaseous component;
g) transferring the powder-containing gaseous component to a
baghouse;and
h) releasing the substantially mercury-free gaseous component of
said sample to the atmosphere.
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An adsorption powder for the removal of mercury and other metals,
dioxins, furans and other organic compounds must be efficient under a range of
conditions. Currently available powders do not function well at high
temperatures
and in high moisture environments, conditions that are favorable to mercury
removal.
High temperatures are necessary for effective removal of contaminants
from soil. Temperatures of about 1800°F are necessary to volatize
organic
compounds, metals and other impurities from the contaminated soil. Mercury
that is
trapped in contaminated soil, however, is most efficiently adsorbed on carbon
at about
300-500°F. The most practical method of cooling a gas stream exiting an
1800°F
oven is to inject water into the gas stream. Water injection cools the gas
stream to a
temperature favorable to mercury removal, but also increases the moisture
content of
the sample, which decreases the efficiency of available mercury adsorption
powders.
The mercury absorbing properties of available powders suffer dramatically in a
high
moisture environment. The adsorption powder of the invention, however,
operates
effectively even in a higher moisture environment.
Experiments with carbon sources showed that coal carbon was superior
to wood carbon for mercury adsorption. Many available adsorption powders use
wood carbon as a component, rather than coal carbon. Cupric chloride was
observed
to significantly enhance the adsorption of mercury from a gas stream and is
the key to
2o the instant invention. Cupric chloride supplies chlorine and activated
copper to the
elemental mercury in the exhaust stream. Elemental mercury reacts with the
chlorine
to form mercury chloride and the activated copper to form a stable mercury
amalgam.
Both forms of mercury are easily captured from the exhaust gas stream. KI3
impregnated carbon was also found to increase mercury adsorption when it was
included in the powder.
Figure 1 shows a schematic diagram of the actual process and equip-
ment used to carry out the invention. Prescreened contaminated feed soil ready
to be
processed 2 is placed within soil cleaning unit 4. The contaminated soil is
heated to
about 900°F or a temperature that will completely volatize the
contaminants from the
soil and generate a gaseous stream, as well as a clean/remediated solid soil
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component. Preferably, soil cleaning unit 4 is a rotary kiln. The gas stream
is then
passed out of soil cleaning unit 4 to dust remover 6, while any solid fraction
of the
feed soil is transferred to clean soil cooling unit 8, where the soil is
cooled and
prepared for reuse. Dust remover 6 is preferably a multi-tube dust collector.
After dust remover 6 removes any particulate matter from the gas
stream sample, the gas stream is passed into the Exhaust Cleaning Unit 10. The
Exhaust Cleaning Unit heats the volatilized contaminates to a temperature of
about
1800°F for a minimum of two seconds retention time, which assures
complete
destruction of any remaining organic or other contaminants. From the Exhaust
Io Cleaning Unit 10, the gas stream then passes through cooling chamber 12
wherein a
water pump (not shown) injects water into the cooling chamber 12 to lower the
temperature of the sample to about 360°F. This cooling process
consequentially
increases the moisture content of the sample.
The high temperature, high moisture gas stream is then contacted to the
15 adsorption powder of the invention, which is stored in adsorbent storage
silo 14 and
injected into the gas stream. This powder formulation is effective in removing
metals,
particularly mercury, and other contaminants.
After the gas stream has been contacted to the adsorption powder,
the powder/gas stream mixture continues on to baghouse 16. The carbon
component
2o of the adsorption powder collects on the walls of bags and acts as a
particulate filter
for the gases leaving the baghouse. Baghouse 16 collects the particulate
mercury-
containing fraction of the adsorption powder mixture, which is transported to
a
suitable bulk storage facility 20 and subsequently removed. The gaseous
fraction is
released to the outside atmosphere throL~gh vent 18, while the remaining dust
25 particulate fraction is handled in a similar manner to the particulate
mercury fraction
of the adsorption powder mixture 20.
EXAMPLES 1-84
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A bench-scale, batch rotary kiln system to simulate the system of
Figure 1 was utilized to conduct and compare various powder mixtures for their
capacity to adsorb vaporous mercury from a gaseous stream. A schematic of the
system 31 is shown in Figure 2. A 4-inch diameter quartz rotary kiln 32 was
utilized
to contain the soil, and an insulated clamshell furnace 33 was utilized to
indirectly
heat the furnace. The 4 inch diameter section of the kiln was 14 inches in
length and
contained raised dimples to provide mixing of the soil sample during rotation
of the
kiln. A variable-speed electric motor 34 and controller rotated the kiln.
Purge gas 35
was metered to the kiln with calibrated rotameters from cylinders. Behind the
rotary
to kiln in the process was a thermal oxidizer 36 (another furnace containing a
quartz
tube). The temperatures within the rotary kiln and thermal oxidizer were
maintained
with separate controllers. After the thermal oxidizer, quench water 37 was
injected
into the gaseous stream to lower the temperature of the hot gases. The high
moisture,
quenched gases were passed through an adsorbent powder filter unit positioned
inside
a temperature-controlled oven 38, wherein vaporous mercury was efficiently
adsorbed
by the powder of the invention. The gases were then directed to scrubbing unit
39
that consisted of 2 impingers containing acidic potassium permanganate.
Several soil samples containing known amounts of mercury were
screened to at 1/a-inch to remove rocks and other large particles. The samples
were
thoroughly blended and divided into approximately 1-kilogram charges. These
soil
samples were found to contain from about 14 to about 16 ppm of mercury.
Several
kilogram samples of Magnus soil, containing from about 0.1 to 0.4 ppm of
mercury
were mixed with the samples containing from about 14 to about 16 ppm of
mercury to
create samples containing from about 4 to about 6 ppm of mercury. The final
samples
were air-dried at less than 120°F to eliminate the majority of free
moisture therein.
The air-dried soil aided in providing consistent performance of the batch
system.
Adsorbent mixtures were prepared by separately weighing each
selected component thereof and blending them together. About 4.0 grins of
adsorbent
mixture per about 1 kg of soil was used in each batch measurement (1 kg of
soil, as
3o received basis, or about 0.88 kg of air-dried soil). The adsorbent mixture
was then
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packed into a 1.5-inch diameter tube (Test Nos. 1-28) or, alternatively,
loaded into a
102 mm x 1.6 mm filter holder (Test Nos. 29-84) and evenly distributed, and
the tube
or filter holder, respectively, was placed inside the filter oven.
The air-dried soil (about 0.88 kg) was loaded into the quartz kiln, gross
and net weights were calculated therefor, and the kiln was positioned within
the
furnace. A small amount quartz wool was inserted into the exhaust gas end of
the
system to filter and trap any dust that might be elutriated from the soil.
Behind the
filter oven was placed 2 impingers, as final gas scrubbers to capture any
mercury
vapors that might pass through the adsorbent powder. About 100 mls of acidic
to potassium permanganate solution was added to each impinger, they were
placed in ice
baths, and connected to the filter outlet with ground-glass connections so the
gaseous
stream would bubble through the solution. Inlet gases were mixed to provide a
composition of 10 vol. % oxygen, 3.2 vol. °7o carbon dioxide, 100 ppm
of nitrogen
oxide, 10 ppm of sulfur dioxide, and the balance nitrogen. The gases were
metered
into the kiln after all of the connections were complete and gas flow was
initiated to
the inlet of the kiln at 4.0 standard liters per minute. The system's units
were pre-
heated to target temperatures before the gas was directed through the thermal
oxidizer, water-quench section, and filter oven. Water addition at the outlet
of the
thermal oxidizer was at a rate of 0.2 ml/min for Test Nos. 1 through 27 and
1.5
mls/min for Test Nos. 28 through 84 (about 30 wt percent moisture in the gas
stream
entering the adsorbent filter).
Unless otherwise specified, the experimental conditions were as
follows:
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Table 1
Parameter Value
Kiln Charge (dry air),0.88
kg
Adsorbent Weight, . 4.0
g
Water Addition, cm/min1.5
Purge Gas Flow, L/min4.0
Unit Temperatures, C
Kiln 480
Thermal Oxidizer 960
Thermal Oxidizer Outlet204
Adsorbent 204
After the target temperatures had been achieved for the gas handling
units, kiln rotation (1 rpm) and heating 480°F (900°C) were
initiated, and water
injection downstream of the thermal oxidizer was also initiated. About 30
minutes
were required to heat the soil to the required temperature, and about 10
minutes after
the soil reached that temperature the experiment was stopped. Throughout the
experiments, temperatures and gas flows were monitored and controlled at their
to desired set points. At the end of each experiment, the treated soil,
adsorbent powder,
and potassium permanganate solution were recovered and analyzed for total
mercury.
A material balance and distribution of mercury were calculated based on
weights and
assay results. Mercury capture presented herein was calculated as the
difference
between 100 and the percent of recovered mercury reporting to the off-gas
impingers.
Tables 2 through 8 present the data obtained from the Test Nos. 1
through 84 utilizing 3 base, adsorbent powder mixtures, as follows:
Powder No. l: 38% carbon + 58% Ca(OH)2 + 4% sulfur
Powder No. 2: 38% carbon + 58°Io Ca(OH)2 + 4°7o sulfur +
10% KMnO~.
2o Powder No. 3: 38% carbon + 62% Ca(OH)2 + 10°lo KMn04
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Additional components (in weight percent) added to the powders are
listed in the tables. For each test run, the soil sample weight, amount of
assay
mercury contained therein, and the total amount of mercury in the sample was
recorded. "Residue" refers to the amount of sample left in the kiln after the
heating
process, and mercury capture percent provides the efficiency of mercury
removal
from the sample. "Hg accountability" is the total amount of mercury calculated
by
material balance.
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CA 02451534 2003-12-19
WO 03/006140 PCT/US02/21120
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CA 02451534 2003-12-19
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-20-
CA 02451534 2003-12-19
WO 03/006140 PCT/US02/21120
Table 9
Absorbent Powder Vapor Mercury Test Numbers
Mixture
Ca ture, % Achievin Ca
ture
38% WCC with KI3 98.7 to 99.5 67, 79A, and
79B
52% Ca(OH)z
10% CuClz
38% WCC 96.7 to 99.0 63, 77,
52% Ca(OH)z 80, 81, a
10% CuClz and 83 ~
38% WCC with KI3 >98.2 64, 78A, and
B
62% Ca(OH)z
35% WCC 95.9 to 96.9 82 v
50% Ca(OH)z 84'~
5% WCC with KI3
10% CuClz
Original Rahway 57.3 and 60.0 29 and 62
Powder Mixture
1/ Seidler Chemical Co. CuClz
2/ Phibro-Tech. Inc. CuClz
WCC = Westates Coal Carbon
-21-
CA 02451534 2003-12-19
WO 03/006140 PCT/US02/21120
In accordance with the tables, Test Numbers 29 and 62 utilized the a
powder without additives (38 wt.% of carbon, 52 wt.% of calcium hydroxide, and
4
wt. % of sulfur), and the mercury capture results were 60 and 57.3 %,
respectively.
The addition of 5% cupric chloride (by weight) of Test Numbers 30, 39 and 40
resulted in mercury capture efficiency ranging from 86.5 to 90.0%. Ten percent
cupric chloride added to the kiln charge, Test Number 33, resulted in a
mercury
capture of 93%. Test Number 32 containing additives of 5% potassium
permanganate
and 5% cupric chloride resulted in a mercury capture efficiency of 93.8%. Five
tests,
Test Numbers 54 through 58 were preformed using soil (containing no mercury)
to spiked with various mercury compounds to achieve approximately 4 to 5
milligrams
of mercury in the kiln burden. Spiking compounds included HgCl2, HgS, HgO,
HgSO~., and elemental mercury, and the adsorbent powder included a 5% cupric
chloride additive. The mercury removal efficiency for these examples ranged
from 83
to 91%.
Test Numbers 37 and 69 (repeat examples) achieved mercury capture
efficiencies of 99.3 and 99.6%, respectively, utilizing Westates coal carbon
impregnated with potassium iodide. Westates coal carbon impregnated with
potassium iodide mixtures, as tested in Tests 64 and 67, provided mercury
capture
efficiencies of 98.3 and 98.7 %, respectively. Test Numbers 79A and 79B
contained
2o an adsorbent powder characterized as containing 38% Westates coal carbon
impregnated with potassium iodide, 52% calcium hydroxide, and 10% cupric
chloride, and the mercury capture increased to 99.6% with the addition of
cupric
chloride the powder.
-22-
