,

ELEMENTAL MERCURY REMOVAL USING A WET SCRUBBER*

KeIIy Martin
Eduardo Gonzalez
Chenn Q. Zhou
Department of Engineering
Purdue University Calumet
Hammond, IN 46323

and

C.D. Livengood
M.H. Mendelssohn

Argonne National Laboratory

Argonne, IL 60439

April 1999

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“Work supportedby the U.S. Departmentof Energy,AssistantSecretaryfor FossilEnergy,under ContractW-31-109-

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Presentedat the 61” Annual Meetingof the AmericanPower Conference,Chicago,IL, April 6-8, 1999,sponsoredby
..- Illinois Instituteof Technology.
-*
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,
 ELEMENTAL MERCURY REMOVAL USING A WET SCRUBBER*

Kelly Martin
Eduardo Gonzalez
Chenn Q. Zhou
Department of Engineering
Purdue University Calumet
Hammond, IN 46323

C.D. IAvengood
M.H. Mendelssohn
Argonne National Laboratory
Argonne, IL 60439

ABSTRACT the mass transfer. Another literature survey was

Mercury (Hg) is a toxic metal that is emitted into the performed on the reaction kinetics of mercury. The
environment by both natural and human activities. Acute information obtained was used to postulate probable
and chronic exposure to mercury and methyl mercury in behavior of elemental mercury in flue gas.
humans results in central nervous system damage, kidney The experimental results obtained at Argonne will be
damage, and even death. Although some Hg emission related to existing wet scrubber technology to determine
sources have been regulated, coal-fired utilities have not the economic feasibility of mercury removal. A cost per
been. In anticipation of federal regulations on mercury pound of mercury analysis will be utilized.
emissions from coal-fired power plants, Argonne National
Laboratory (ANL) has designed a flue gas simulation INTRODUCTION
system to study the removal of elemental mercury. The
Concerns about mercury emissions into the
simulated flue gas enters the system and combines with
atmosphere are rapidly increasing. Results of numerous
the inlet mercury vapor (from a calibrated permeation
studies are shedding light on what is still a relatively little
tube), carried by nitrogen gas. This combined gas
known subject. Regulations are already in place for
continues past the flow meter and the pressure gage to the
limiting mercury emissions from municipal solid waste
reactor inlet. Inside the reactor chamber, the flue gas is
(MSW) boilers. However, coal-burning electric utilities,
sprayed with NOXSORB@, a chloric acid solution, which
which are a major source of mercury emissions, have not
reacts with elemental mercury. The amount of reaction
been regulated. As part of an effort to control mercury
(oxidation) of elemental mercury is important since
emissions, the U.S. Congress mandated that the U.S.
mercury in an oxidized form is highly soluble, In this
Environmental Protection Agency (EPA) conduct an
form, the Hg can be picked up downstream by a wet
extensive study on mercury emissions
scrubber from fossil-fuel burning utilities.14
One of the objectives of this paper is to look
Experiments on mercury removal from flue gases
specifically at coal burning utility plants in an effort to
have been conducted at ANL, with the participation of a
assess current mercury control systems and to evaluate
senior design team from Purdue University Calumet.
potential designs for new mercury emission controls.
Temperature variations ranging from room temperature to
One of the first major problems encountered with attempts
350”F have been studied. Other parameters, such as the
to control Hg emissions from coal-fired electric utilities is
concentration of NOXSORB@, were also tested.
that after combustion, mercury is a volatile trace element
Furthermore, pump speed and sprayer droplet sizes of the
that exists as a vapor passing through the existing control
NOXSORB@ solution were studied.
devices and straight into the atmosphere. In fact, there is
A literature survey on the current and proposed
still considerable uncertainty about the types and
mercury control legislation, along with the exisfing control
concentrations of individual mercury compounds in the
technologies, has been performed as part of the senior
flue gas. According to Huang et al., “the lack of
design project. With guidance from ANL, an
information . . . makes a credible risk assessment
understanding of the simulation system has been
impossible... “.5
developed. This information has been used to determine

Work supportedby the U.S. Departmentof Energy,AssistantSecretaryfor Fossil Energy,under ContractW-31-109-ENG-38.

*
 The U.S. llep~ment of Energy has responded to Lab Scrubber
these concerns by sponsoring research at Argonne The lab scrubber is a bubbler type. The lab scrubber
National Laboratory (ANL) on elemental mercury is filled with 200 mL of a water and sodium hydroxide
emissions from coal-fired utilities. ANL has developed an (NaOH) solution. This solution imitates the process found
elemental mercury removal process utilizing existing wet in industrial scrubbers. The velocities of the bubbles
limestone scrubbers and NOXSORB@, a chloric acid reflect the residence time, which directly affects the
so1ution,7 Additional solutions of the reagent amount of HgOremoval obtained.7
NOXSORB@ are injected into the flue gas stream prior to
scrubbing. The intent is to oxidize elemental mercury into Laboratory Procedure
a more soluble form that can then be captured in the The following simplified procedure was used to
scrubber slurry. This paper details the experimental conduct the experiments utilizing the atomizer at room
methodology, mass balance, and the chemical reactions temperature and elevated temperatures:
involved. 1. The flue gas constituents are fed into the system ,and
the constituents are measured by using Beckman
APPARATUS AND PROCEDURE instruments. Typical flue gas concentrations are 14-”
16’%COZwith a 99.5% purity, 300-450 ppm NO with
A design schematic of the lab-scale HgO removal
99.0% purity, and 650-750 ppm SOZ with 99.98%
process utilizing an ultrasonic atomizer is shown in Figure
purity.
1. As depicted in the diagram, the simulated flue gas
enters the system and combines with the N2 gas stream 2. The Teflon@ gas tubing is then heated for high-
that is used as a carrier gas for the elemental mercury. temperature tests.
This combined gas stream continues past the flow meter 3. A solution of NOXSORBTM and distilled water is
and the pressure gage to the reactor inlet. The reactor prepared and primed into the atomizer. Liquid flow
simulates the ductwork prior to scrubbing in a full-size rates through the atomizer were varied, depending on
operation. The residence time in the chamber is ranged the desired flow rate.
from 6 to 10s according to Livengood.G Inside the reactor 4. A solution of approximately 0.3 g of sodium
chamber, the flue gas is bombarded with reactant by an hydroxide (NaOH) in 200 mL of distilled water is
ultrasonic atomizer. The atomizer mists the reactant for prepared as the bubbler liquor. This liquor mimics
an even distribution within the reactor and simulates a co- the liquor found in the typical wet scrubber.
flow scrubber process. The gas then enters the bubbler 5. An elemental mercury permeation tube is placed in a
where the oxidized mercury is captured. The HgOlevels Nz gas stream at 70”C. This tube is calibrated to
found in both the bubbler and the sump indicate the release 3.57 Bg of Hg/15 min at 70”C.
amount of HgOremoved from the flue gas. 6. Typical gas flow rates for the nitrogen-mercury
stream are 4.8 L/rein, the typical gas flow rate for the
NOXSORB@ Injection total gas stream, including the nitrogen-mercury, is
6.0 L/tin.
The NOXSORB@ is sprayed into the flue gas stream
7. The NOXSORB@ is injected into the gas stream for
prior to scrubbing on a vertical length of simulated
15 min.
ductwork. The NOXSORB@ is injected into the reactor
8. Liquid samples from both the sump and bubbler were
in the middle of the chamber with the ultrasonic atomizer.
saved for each test and analyzed for mercury content.
The mist is assumed to have a linear flow to simplify the
9. Mercury analyses were performed by a standard cold-
analysis of the spray. The volumetric gas flow rate of the
vapor atomic absorption spectrophotometric method
combined gases into the reactor is approximately 6 L/rein.
(U.S. EPA Method 7470A, SW-846). The estimated
This volumetric gas flow rate is assumed constant
accuracy for this method is MOYo or kO.02 @.+
throughout the system. However, adjustments are
whichever is greater.
necessary during the test cycle to maintain steady flow.
The reactor chamber diameter is 3 in. and the gas
RESULTS AND DISCUSSION
lines to and from the reactor have inside diameters of 3/8
in. The residence time is the time that a single particle of
Mass Analysis
NOXSORB@ would spend inside the reactor with the flue
Initial baseline tests were performed to validate the
giis. The average distance for the residence time is 3.’75
in., which is one-half the total height of the reactor. absence of residual mercury in the simulation system.
These tests used water as the oxidizing agent. Then, a
series of tests was run to determine the removal
effectiveness of NOXSORB@ injection at room
temperature. The lab system set-up was analyzed for mass
balance of the HgO. The HgOis carried by a nitrogen (Nz) significantly aid in the removal efficiency, even at low
gas stream and combined with the simulated flue gas. The NOXSORB concentrations.G
simulated flue gas temperatures were both ambient and A new method was implemented to introduce the
heated to simulate actual temperatures. The reagent NOXSORB@ into the gas stream. The process
solution, NOXSOREN9, was then injected into the gas description is proprietary; however, the results from these
stream to oxidize the Hg0. The sump condensate and the experiments are found in Table 2. These results are
bubbler solution were collected and analyzed for HgO significant because of the very low volumes of
content. The following mass analysis demonstrates thk NOXSORB@ required for maximum HgO and NO
process. A description of the system components is removal efilciencies. These tests will be duplicated in the
presented as product-in equals product-out. The fwst law future to verify the results. The addition of sulfur dioxide
of thermodynamics, which states that mass is constant, is did not significantly affect the removal efllciencies of this
applied in Equation 1. new process.
Table 3 compares the results of ambient and high-
(mercury)+(flue gas)+(reagent) = temperature tests for which the ultrasonic atomizer was
(condensate)+(scrubber content)+(exit gas) (1) used. The 1% NOXSORB@ concentrations, in
conjunction with the elevated temperature, removed 51 YO
The total amount of HgOcollected from the sump and more HgO and 3090 NO. The 4% NOXSORIM3
the bubbler was calculated for each test. This total was concentration test for the elevated temperature removed
then divided by the total HgOcalibration of 3.57~g, which 66?10more HgOand 77% more NO. Therefore, it appears
indicates the percentage of HgOcaptured. Trace amounts that the elevated temperatures required less NOXSORB@
of oxygen (02) were also present in the flue gas; however, solution for a significant increase in the removal
it was not added to the system. Since 02 would only efficiencies.
improve the oxidation of Hg0, the actual 02 found in
typical flue gas content would not retard the results Chemical Reaction Analysis
obtained from this process. To make an assessment of the behavior of elemental
The mass balance of the process is analyzed by using mercury in flue gas from coal-fired power plants, all the
the experimental results in the Data Analysis section of variables must be defined. The fust step is to determine
this report. Exact stoichiometric chemical equations the gases produced when coal is combusted. According to
regarding the system components are beyond the scope of Hall et al., all combustion processes generate basically the
this project. Therefore, a simplified analysis of the following gases: N2, 02, H20, CO, and NO.. They add
important reactions is discussed in the Chemical Reaction that other gases (such as S02, HC1, C12,H2S, and NH3) are
Analysis section of this report. also present however, their concentrations are dependent
on the type of coal combusted and the temperature
Data Analysis conditions of the furnace.g
Figure 2 represents the HgO and Nitric Oxide(NO) According to Mendelssohn and Livengood, the
removal results obtained for gas streams of N2 and C02 at reactions of NO and NOXSORB@ produce hydrochloric
room temperature. The HgO removal effectiveness and nitric acids, which may cause the improved Hg
increases with increasing NOXSORB @ concentrations. removal when NO is in the gas stream. An explanation is
The test with the lowest concentration of NOXSORIXD that since nitric acid dissolves liquid mercury, the formed
removed only !)qo of the mercury and an immeasurable nitrous/acid may oxidize the HgO.They add that nitric acid
amount of NO. Therefore, at room temperature, the is commonly used and in combination with HC1 in the
process would be considered too expensive to remove a laboratory protocols for the analysis of mercury
substantial amount of mercury. compounds and in cleaning laboratory equipment of
It was then decided to conduct experiments at mercury residues. This conclusion is supported by
increased flue-gas temperatures to investigate removal Llndberg and Stratton when they show that trends in
effectiveness under real-world conditions at a typical coal- mercury speciation may suggest that peak concentrations
burning power plant. The results for the elevated of NOX and S02 correlated with peak concentrations of
temperature testing using the ultrasonic atomizer are reactive gaseous mercury (RGM).
shown in Table 1. A significant increase in the HgO In addition, a different pattern of behavior was found
removal was demonstrated using the 1% solution, with for solutions containing chlorine or chlorine compounds.
minimal NO removal. The 4% concentration of the Chlorine solutions showed no dependence on
NOXSORB yielded very good results; however, even at concentration when nitric oxide and sulfur dioxide were
these concentrations, the economics are still unreasonable. absent, indicating that the mercury-chlorine reaction is
These results indicate that the elevated temperatures probably slow without the presence of a catalyst. Addition
of nitric oxide to the gas stream greatly increased the based on the wet limestone, droplet-type scrubber system
amount of HgOremoval. with a reactant introduced prior to scrubbing and after the
This increase in the removal may have been due to electrostatic precipitator.
the formation of an intermediate compound, such as An understanding of the lab-scale mercury removal
nitrosyl chloride (NOCI), which could react rapidly with process developed by ANL was established. The physical
the HgO. attributes of the lab processes were identified, and the
process flow diagram was developed. The necessary
Hg(g) + NOCl(g)~ HgClz(g) + NO(g) (2) equations required to analyze the duct injection and the
bubbles in the lab scrubber were developed. Fhdy, a
ANL’s conclusion for the reaction of Hg in the presence simplified lab procedure was developed.
of NO is that NOCI probably reacts faster with HgOthan Additional analysis was performed for the mass
does Clz. It is believed that HgOreacts faster with Clz if balance of the mercury in the system. The majority of the
there is a catalyst (such as NO) or, as mentioned before, a mercury was captured in the sump condensate, with most
product of the NO and NOXSORB@ reaction. More of the remainder collecting in the slurry. The chemical
research is required to determine the exact mechanisms reaction kinetics were investigated, and the evidence
involved.8-*4 suggests that the majority of the mercury reactions occur
in the vapor phase. The results of the NOXSORB@
Mercury Removal Efficiency experiments showed the addition of NO appears to
According to the Olin Corporation, the cost of enhance mercury removal, suggesting that there is an
NOXSOIUK3 is approximately $0.7/lb. Assuming that intermediate reaction.
Fhally, a simple economic analysis was performed
NOXSORBQ3 has the same density of water (0.997
on the basis of the amount of NOXSOREKB necessary to
glcm3), the NOXSORB@ pounds per one liter can be
accomplish a significant mercury removal from flue gas.
calculated by using Equation 3.
This process, which used a new method of NOXSORB@
(0.997 g/cm3) x (1 cm3/0.001 L) x (0.0022046 lb/g) injection, removed 100% of the mercury emissions (80%
= 2.198 lb/L (3) of the NO emissions) at a cost of $24,500 per pound of
mercury removed.
The cost per pound of mercury removed is estimated
REFERENCES
at $25,000 for optimal conditions. The goal of this
project was to achieve a $50,000 cost per pound of 1. Anonymous, Mercury and Compound, United States
mercury removed with 90% removal rate. The process Environmental Protection Agency, Feb. 13, 1998,
achieved less than half of the proposed cost per pound. httu://wwwe~a.rov/ttnuatw Vhltheffmercurv.htlrn.
Therefore, the new method is economically feasible. 2. Mercury Study Report to Congress: White Paper,
Additional savings can be obtained from the NO removal. United States Environmental Protection Agency,
Capital costs associated with the system will vary February 13, 1998, htttx//www.e~a. ~ov/airmomn/oar/
depending on the existing system components already in merwhite.htnd.
place. The system must be custom-engineered on the 3. French, C.L., et al., Study of Hazardous Air Pollutant
basis of the following: size of boiler; type of coal Emissions from Electric Utility Steam Generating
combusted; flue-gas volume; auxiliary equipment; and Units - Final Report to Congress, U.S. Environ-
federal, state, and local regulations. The associated mental Protection Agency, 453/R-98-004a, February
maintenance and operating costs are also not yet 1998.
identifiable, as the system components are not yet 4. “Mercury in the Environment,” Electric Utility Trace
established. Many other factors must be considered in the Substances Synthesis Report, Volume 3: Appendix
implementation of this process (i.e., waste management, D, EPRI TR-104614-V3, Electric Power Research
solution regeneration, scrubber slurry contamination, Institute, PaIo Alto, California, 1995.
corrosion of the system components, and monitoring of 5. Huang, H.S., et al., Emissions of Airborne Toxics
the mercury emissions). ji-om Coal-fired Boilers: Mercury, Energy Systems
Division, Argonne National Laboratory Report
CONCLUSION ANL/ESDf17vl-35 (September 1991).
Wet limestone scrubbers were found to be the most 6. Llvengood, C.D., and M.H. Mendelssohn, Improved
common flue gas desulfurization (FGD) process used. Mercwy Control in Wet Scrubbing through Modified
FGD systems have proven to be the most effective in Speciation, EPRI-DOE-EPA Combined Utility Air
reducing HgOemissions (up to 50%). Design parameters Pollutant Control Symposium, Washington, D.C.
for a typical coal-fired utility FGD scrubbing system were (August 25-29, 1997).
 .
.

7. Droste, R.L., Theory and Practice of Water and 12. Livengood, C.D.; Mendelssohn, M.H., “Investigation
Wastewater Treatment, John Wiley & Sons, Inc., of Modified Speciation For Enhanced Control of
New York, 1997, pp. 372. Mercury: Advanced Coal-Based Power and Environ-
8. Hall, B., Schager P., Lindqvist O., Chemical mentrd Systems ’98 Conference, Morgantown, WV,
Reactions of Mercury in Combustion Flue Gases, July 1998,
Water, Air and Soi[ Poliution, 1991,56:3-14. 13. Mendelssohn, M.H., and C.D. Llvengood, “Reactions
9. Carey, T.R.; Hargrove, O.W.; Rhudy, R.G., Enhanced of Gaseous, Elemental Mercury witII Dilute Halogen
Control of Mercury in Wet FGD Systems, Pittsburgh Solutions,” 212th National Meeting of the American
Coal Conference, U.S. Department of Energy, EPRI, Chemical Society, Orlando, Florida (Aug. 25-30,
httD://www.Retc.doe.~ov/docs/~itclcon/fgd.html, 1998. 1996).
10. Galbreath, K.C.; Zygarlicke, C.J. Environmental 14. Lindberg, S.E., Stratton, W. J., “Atmospheric
Science & Technology, 1996,30:8,2421-2426. Speciation Concentrations and Behavior of Re-active
11. Kaczur, J.J., Oxidation Chemistry of Chloric Acid in Gaseous Mercury in Ambient Air,” Environmental
NOX/SOXand Alr Toxic Metal Removal from Gas Science and Technology, 1998, 32, 49-57.
Streams, AIChE 1996 Spring National Meeting,
1996, New Orleans, LA.

TABLE 1 Elevated Temperature Test Results

NOXSORB@ HgO NO
CONCENTRATION (%) REMOVAL (%) REMOVAL (%)
1 I 60 I 30
4 95 83

TABLE 2 New Method Test Results

FLUE-GAS HgO NO
COMPOSITION REMOVAL (%) REMOVAL (%)
N2 + HgO+ COZ+ NO 100 80
Nz + HgO+ COZ + NO + SOZ 87 92-97

TABLE 3 Comparison of Ultrasonic Atomizer Tests

NOXSORB@ HgO NO
CONCENTRATION (%) REMOVAL (%) REMOVAL (%)
AMBIENT 350”F AMBIENT 350”F
1 9 60 -- 30
4 29 95 6 83

*
.

FIGURE 1. Lab Process Flow Diagram.

— %HK(0)RemovaI ..*.. No R~*~v~l

100%
90%
80%

20%
10%
o%
1% 4% 1o% 20% 40%
NOXSORBConcentrationin Solution(mL)

FIGURE 2. HgOand Nitric Oxide Removal Efficiencies.