ASH GROVE CEMENT GOMPA_NY

lo•l CODY STREET OVERLAND PARK, KANSAS 66£10 PHONE 913 /451-8900

FAX 913 /451-1686 F. (t"RAN) L. STI:•EI'I'NAN VICE PRESIDENT

ENVIRONMENTAL

AFFAIRS WRITER'S ©IRECT LINE

BI96057 October 1, 2007 Keith Barnett Office of Air Quality

Planning

and Standards Minerals and Inorganic

Chemicals

Group Mail Code C504-05 Research Triangle

Park, NC 27711 Re: Dear Keith,

Ash Grove Cement

Company

Durkee,

Oregon

Enclosed is a copy of the Mercury

Control

Slipstream

Baghouse

Testing at Ash Grove's

Durkee

Cement

Facility". Please call me if you have any questions

regarding

this test program Sincerely,

Vice President

Environmental

Affairs EnclosureMERCURY CONTROL SLIPSTREAM BAGHOUSE TESTING AT ASH

GROVE'S

DURKEE

CEMENT FACILITY Prepared for: Ron Vidergar Ash Grove Cement

Company i011 Cody Street Overland Park, KS 66210

Prepared

by." Michael L. Jones John P. Kay Brandon M. Pavlish Kevin C. Galbreath Energy & Environmental

Research

Center University of North Dakota 15 North 23rd Street, Stop 9018 Grand Forks, ND 58202-9018

September 2007TABLE OF CONTENTS

LIST OF FIGURES iii LIST OF TABLES iv NOMENCLATURE v EXECUTIVE SUMMARY vi 1.0 2.0 INTRODUCTION BACKGROUND 2.1 Process

Overview 2.2 Mercury 2 2.3 Previous

Mercury

Studies for Cement

Kilns 3 2.4 Mercury

Control

Strategy 4 3.0 PROJECT

OVERVIEW 5 3.1 Goals and Objectives 5 3.2 Approach/Work

Plan 5 4.0 FACILITIES

AND EQUIPMENT

DESCRIPTION 6 4.1 Description

of Ash Grove Durkee Facility 6 4.1.1 Raw Material

Handling 6 4.1.2 Raw Mill 6 4.1.3 Fuel Systems 6 4.1.4 The Pyroprocess 6 4.1.5 Cement

Mill 7 4.1.6 Cement

Storage and Shipping 7 4.1.7 Description

of the Main Air Pollution

Control Device 7 4.2 Description

of the EERC Slipstream

Baghouse 7 4.3 Mercury

Monitoring 9 4.3.1 Main Stack Mercury

Monitor 9 4.3.2 Slipstream

Fabric Filter Baghouse

Mercury

Monitor 9 4.4 OH Method

Flue Gas Mercury

Measurements 10 4.5 Carbon Trap (EPA Method

30B) Mercury

Measurements 4.6 Powdered

Activated

Carbons 11 4.7 Stack RATA Testing II 4.8 Fixed-Bed

Testing 12 5.0 RESULTS

AND DISCUSSION 12

Continued...TABLE OF CONTENTS

(continued)
5.1 Slipstream

Baghouse

Operation 12 5.2 SSBH Baseline

Testing 13 5.2.1 Raw-Mill-On

Baseline

Period 13 5.2.2 Raw-Mill-Off

Baseline

Period 16 5.3 Parametric

Testing 18 5.4 Stack Hg Measurement 29 5.5 Analytical

Methods

and Procedures-

Their Applicability

at the Durkee Facility

35 5.6 Main Stack RATA Testing 36 5.7 Fixed-Bed

Testing 37 6.0 CONCLUSIONS 37 6.1 SSBH Testing 37 6.2 Performance

Monitoring 39 6.3 Fixed-Bed

Option 39 PERSONNEL RESUMES Appendix

A EXAMPLE CALCULATIONS Appendix

B SLIPSTREAM BAGHOUSE

MM DATA AND TEST DESCRIPTION Appendix

C QUALITY ASSURANCE/QUALITY CONTROL Appendix

D MAIN STACK

MM DATA Appendix

E MAIN STACK

DAILY

AVERAGE

HG CONCENTRATIONS Appendix

F NATIVE MERCURY

CAPTURE

STATISTICAL

EVALUATION

AND SUMMARY OF MM VARIANCE Appendix

G CALCULATION OF A MASS WEIGHED

POTENTIAL

ANNUAL REMOVAL EFFICIENCY Appendix

H

iiLIST OF FIGURES
Cement manufacturing

process basic flow diagram 2 2 SSBH, trailer, and control room 8 3 Schematic

of the SSBH showing

the locations

of MM sampling

and carbon injection

10 4 Raw-mill-on

baseline

results comparing

MM, carbon traps, and OH method 15 5 Raw-mill-off

baseline

results comparing

the MM to the carbon trap results 17 6 PAC injection

results for the injection

of DARCO

Hg at lbEVlacf 19 7 PAC injection

results for DARCO

Hg for the injection

of 3 and 5 lb/Macf 21 8 PAC parametric

testing results performed

at an A/C ratio of 4 with standard

PPS bags 22 9 Bag type comparison

showing

their effectiveness

in regard to Hg removal

efficiencies

24 10 Membrane/fiberglass bags parametric

testing results showing

effects of varying A/C ratio 25 11 Membrane/fiberglass bag parametric

testing results showing

effects of varying PAC injection

rate 26 12 Raw-mill-off

injection

testing with membrane/fiberglass bags at an A/C ratio of 8

27 13 Full-scale

carbon injection

results 28 14 Graphical

comparison

of MM, carbon trap, and OH method for April 15, 2007

30 15 Comparison

MM graphs for April 23 and May showing

the variability

of HgtotaI and Hg ° output 32 16 Average

Hg concentration

during raw-mill-on

conditions

over the entire test period compared to various specific days 34 17 Stack MM data of raw' mill outage overnight

April 15 through

16 35LIST OF TABLES
Table I. Brief Description

of the Carbons

Tested During Parametric

Testing Through

the SSBH Table 2. Results

from Carbon

Trap and OH Method

Testing

During Raw-Mill-On

Baseline Testing

........................................................................................................................................... 14 Table 3. Results of Carbon Trap Testing During Raw-Mill-Off

Baseline

Testing 18 Table 4. Comparison

of Bag Type Results 24 Table 5. Comparison

of Sampling

Methods

Showing

Difference

of MM with Carbon Trap and OH Method

................................................................................................................................... 30 Table 6. Stack Emission

Carbon Trap Data 31 Table 7. Comparison

of Process Data for April 23, 2007, and May 1, 2007 33 Table 8. RATA Test Results 36

ivNOMENCLATURE
A/C APCD acfm ASTM CVAAS EERC EPA ESP FF(g) Hg Hg

° Hg 2÷ Hgp Hgtotal IGS ILC lbMacf MM NESHAP NIST Nm • ODEQ OH PAC PPS RATA SEA SLC SSBH std. dev. TDF •.tg

air-to-cloth air pollution

control device actual cubic foot per minute ASTM International

(formerly

American

Society

for Testing and Materials) cold-vapor atomic absorption

spectroscopy Energy & Environmental

Research

Center U.S. Environmental

Protection

Agency electrostatic precipitator fabric filter gas mercury gaseous elemental

mercury gaseous inorganic

mercuric

compounds particle-bound mercury total mercury

for Ontario

Hydro measurements,

it includes

Hg °, Hg 2+, and Hg(p), whereas

for mercury

monitor

measurements,

it includes

Hg ° and Hg 2+. inertial gas separation in-line calciner pound (0.454 kg) million actual cubic feet mercury monitor National Emission

Standards

for Hazardous

Air Pollutants National Institute

of Standards

and Technology normal cubic meter (20°C, 7% O,, dry, at atm) Oregon Department

of Environmental

Quality Ontario Hydro powdered activated

carbon polyphenylene sulfide relative accuracy

test audit sorbent enhancement

additive separate-line calciner slipstream baghouse standard deviation tire-derived fuel microgramMERCURY CONTROL

SLIPSTREAM

BAGHOUSE

TESTING

AT ASH GROVE'S DURKEE CEMENT

FACILITY
EXECUTIVE SUMMARY In early 2007, Ash Grove engaged

the Energy & Environmental

Research

Center (EERC) to assist the company

in assessing

and evaluating

mercury

(Hg) emission

controls

suitable

for
use on a cement kiln. Because

no other cement plant is known to have installed

emission

controls designed to reduce Hg emissions,

this project

was highly experimental.

The EERC first identified powdered

activated

carbon

(PAC) injection

as the most promising

technology

for controlling Hg from cement plants. The EERC then arranged

for the temporary

installation

of a fabric filter (FF) slipstream

baghouse

(SSBH) and PAC injection

at the Durkee Plant. Thispilotscale control system received

a small slipstream

of air off the main stack (-1% of the total main stack exhaust

gas), thus enabling

the EERC to perform

a series of tests over 6 weeks under realistic conditions. The overall goal of this project was to perform

parametric

testing on a slipstream

of actual flue gas from Ash Grove's

Durkee

cement

facility to gain an understanding

of how various operating and design parameters

are likely to impact Hg control for the Durkee cement plant as well as to determine

whether

a predicted

I-Ig control efficiency

could be established.

Carbon type, FF bag type, PAC injection

rate, and air-to-cloth

(A/C) ratio were all evaluated

during the pilot test. Mercury

monitors

(MMs) were used in conjunction

with carbon traps and Ontario Hydro method tests to provide

data on Hg emissions.

Based on these data, key design parameters for a full-scale

Hg control

installation

were assessed,

and a predicted

control efficiency

was established for the pilot-scale

system. The EERC testing identified

clear design choices

for use in a full-scale

Hg control installation at the Durkee

facility.

Monitoring

during

the pilot test period demonstrated significant variability

over short periods of time (e.g., hourly, daily) in both total mass of Hg and form of Hg (Hgtota• vs. Hg °) at the SSBH inlet. This variability

appears

to be irrespective

of kiln operating conditions.

Despite

this variability,

clear design choices

were identified

for use in developing a full-scale

Hg control installation.

The pilot study demonstrated

that the type of activated carbon used in the PAC injection

system makes no material

difference

in controlling Hg emissions

from the Durkee

cement

kiln. While studies at coal-fired

power plants have indicated that the use of halogen-treated

PAC can result in higher Hg control efficiencies,

testing
on the Durkee

exhaust

gas indicated

that untreated

carbon provides

equivalent

control

to halogen-treated carbon. This is believed

to be due to the low sulfur levels in the Durkee cement kiln exhaust

gases as compared

to coal-fired

power plants. The different

FF bag types perform comparably, but the fiberglass

with membrane

bags were deemed

most appropriate

because

of their ability to withstand

the higher temperatures

that can occur during kiln upsets. The A/C ratio testing documented

that high Hg control efficiencies

occur at levels in the 6 to 8 range. Hg control efficiency

dropped

oft materially

at levels below that range, and Hg control efficiency did not change materially

at levels higher than this range. PAC injection

rates ,,,,.ere varied during raw-mill-on conditions

between

and 5 lb/Macf.

Significant

increases

in Hg control efficiency
were realized

during this testing by increasing

the PAC injection

rate from to 3 lb/Macf:insignificant changes

in Hg control efficiency

typically

occurred

when the PAC injection

rate
was increased

from 3 to 5 lb/Macf.

With the parameters

in the optimal

ranges/rates,

90% Hg removal efficiencies

were routinely

achieved

by the pilot-scale

system during raw-mill-on conditions. Testing was also performed

during raw-mill-off

conditions.

It is necessary

to shut down the raw mill for short periods each week resulting

in kiln exhaust

gas being routed directly

to the main stack baghouse.

During these time periods mercury

levels are elevated--particularly during the first hour after the raw mill is shut down. PAC injection

into the SSBH during raw-mill-off conditions resulted

in a slightly higher Hg control efficiency

at 5 lb/Macf

than at 3 lb/Macf

and injection at 3 lb/Macf

was significantly

higher than at lb/Macf.

PAC was also injected

into the main stack baghouse

during raw-mill-off

conditions

with significantly

higher Hg control efficiency at 5 lb/Macf

than at 3 lb/Macf.

The average

Hg removal

efficiency

during the SSBH and main stack testing at 5 lb/Macf

was 63%. A PAC injection

rate of 10 lb/Macf

was tried for a short period on the SSBH only and the HG removal

efficiency

increased

to 88%. Injection

at the 5 lb/Macf

rate appears

warranted

during raw-mill-off

conditions.

However,

it is unclear

that injecting PAC at 10 Ib/Macf

during raw-mill-off

conditions

would perform

materially

better in a full-scale installation

that had reached

equilibrium

conditions

and so is unlikely

to justify the additional cost, equipment

wear and waste generation.

It is recommended

that the PAC injection system be sized capable

of injecting

up to 5 lb/Macf

during raw-mill-off

conditions

with testing to determine

whether

injection

at that rate is necessary

beyond the first hour after shutting

down the raw mill. Based on the 6 weeks of testing performed

using the PAC injection

installation

and SSBH, the EERC recommends

that a full-scale

Hg control installation

for the Durkee

cement kiln be designed with the following

parameters:

Parameter PAC Type

Design Criteria Untreated carbon
Bag Type

Fiberglass w/membrane
A/C Ratio

6 to 8
Injection Rate

3 lb/Macf

(raw mill on) 5 lb/Macf

(raw mill oft')

Comments Untreated

PAC performs

comparably

to halogen-treated PAC, while avoiding potential environmental

issues associated with use of halogens. All bags performed

comparably,

but fiberglass with membrane

withstands

higher temperatures. Lower A/C ratios resulted in lower control efficiency. Increasing

A/C ratio over this range results in higher energy consumption without increased

control efficiency. Elevated PAC injection

rate duringrawmill-off conditions

may not be necessary after first hour.

viiThe EERC believes

that a Hg control

installation

design based on these parameter selections will provide

optimal

Hg control for the Durkee cement kiln. The pilot test indicates that a 90% Hg control efficiency

should be achievable

on an annual average

basis during the approximately 85% of the time that the raw mill is operating.

The weighted

average

Hg control efficiency across all operating

conditions

should be approximately

77%. However,

the EERC has found that pilot test results are not always reproducible

in full-scale

installations.

Therefore,

we caution against assuming

that a properly

designed

full-scale

Hg control system will necessarily be capable

of consistently

reaching

these Hg removal

rates. We also note that a well-designed installation will vary in control efficiency

over the short term and that control efficiency

should be evaluated

based on long-term

average

performance.

Because

a PAC injection

installation

has not been previously

installed

to control cement kiln Hg emissions,

a full-scale

installation

will require a period for optimization.

The achievement

of 90% control efficiency

(raw mill on) and 77% control efficiency

(weighted

average),

even if it is appropriate

for a full-scale

installation, may take 12 to 18 months

to consistently

reach. Therefore,

the EERC recommends

that if Ash Grove proceeds

with a PAC injection

Hg control

installation

as described

above, that the company plan on 18 months to optimize

equipment

performance.. The full-scale

Hg control

installation

will require periodic

testing to document

control performance. Currently,

MMs are not commercially

available

that could be utilized

in a cement kiln stack, and no approved

relative

accuracy

testing audit (RATA)

method

exists to perform

a RATA for a MM operating

in the environment

presented

by the Durkee cement kiln main stack. Therefore, the EERC does not recommend

the use of MMs for tracking

control

system performance. The use of carbon sorbent traps worked

very well during the pilot test with results comparable to the Ontario

Hydro method

and MM measurements.

Carbon sorbent traps provide
an excellent

means of routinely

checking

Hg air pollution

control device performance

and are recommended for use both during the optimization

period and for subsequent

periodic

testing. The EERC planned

to evaluate

a fixed-bed

Hg control

installation

during the PAC injection pilot study. The fixed-bed

test was not successful

because

of problems

with the equipment. Given the lack of study of fixed-bed

Hg controls

for systems

of the type and scale of the Durkee cement kiln, the EERC cannot recommend

consideration

of this control technology

at this time.

viiiMERCURY CONTROL

SLIPSTREAM

BAGHOUSE

TESTING

AT ASH GROVE'S DURKEE CEMENT

FACILITY
1.0 INTRODUCTION Ash Grove Cement

Company

(Ash Grove) operates

a cement-manufacturing plant located in Durkee,

Oregon.

This plant emits mercury

(Hg) that naturally

occurs in the plant's raw materials and, to a much lesser extent, fuels. In early 2007, Ash Grove engaged

the Energy & Environmental Research

Center (EERC)

to assist it in assessing

and evaluating

Hg emission controls suitable

for use on a cement kiln. To Ash Grove's

knowledge,

no cement kiln is known to have installed

emission

controls

intended

to remove

Hg. Therefore,

this research

effort has sparked national

interest. The EERC has prepared

the following

report outlining

the evaluative

process

that it has engaged in over the past 6 months.

Because

no other cement plant is known to have installed emission controls

designed

to reduce Hg emissions,

this project was highly experimental.

The EERC identified

powdered

activated

carbon (PAC) injection

as the most promising

technology for controlling

Hg from cement plants and fixed-bed

carbon as a possible

alternative

technology. The EERC then arranged

for the temporary

installation

of a fabric filter (FF) baghouse

and a PAC injection

installation

at the Durkee

Plant as well as a fixed-bed

carbon unit. Thesepilotscale control installations

received

a small slipstream

of air off the main stack and enabled

the EERC to test different

PAC types and injection

rates under realistic

conditions.

The information gathered and conclusions

drawn from those data are presented

in this report.
2.0 BACKGROUND 2.1 Process

Overview The cement-manufacturing process

is a large industrial

process

that includes

several processing steps, beginning

with quarrying

raw materials,

preparing

material,

and pyroprocessing the raw mix in the cement kiln system.

Figure 1 shows the basic flow diagram for the cement-manufacturing process.

The process

uses large quantities

of raw materials

(rock) to form clinker,

the intermediate

product

of cement.

The pyroprocessing

step includes

heating the raw mix to temperatures

in excess of 2750°F

in the kiln system,

which is fired with large quantities of fuel to provide

the energy required

for processing

the kiln feed. Fuels are delivered to multiple

locations

in the kiln system in order to deliver the energy at the most effective location for efficient

manufacturing.

Both the raw materials

and the fuel that is used contain minute concentrations

of Hg, which can become

part of the stack emissions

when heated in the kiln system to the high temperatures

necessary

to produce

quality clinker. The Hg is found to be ubiquitous in the raw materials

and fuels used to produce

cement.

As is typical for naturally occurring materials,

there is normal

variability

in the concentrations

of Hg found in these materials.EERC JK30394 CDR Raw Material Stockpiles

and Crushing

m•=• • Preblending and Storage Raw Milling

Burning and Homogenization Cement Milling

and Shipping Figure 1. Cement

manufacturing

process basic flow diagram.
The cement-manufacturing process

includes

complex

physical

and chemical

reactions

that occur during the pyroprocessing

in the kiln system.

The kiln system at Ash Grove's

Durkee facility is a preheater/precalciner system,

which includes

the rotary kiln, a preheater/precalciner tower, and the associated

air pollution

control system. The raw materials

are mined, ground,

and mixed to the appropriate

chemical

consistency

prior to being fed to the kiln system.

The materials are heated in the kiln system to temperatures

that achieve

the appropriate

chemical reactions that result in a quality clinker product.

The facility is equipped

with an in-line raw mill, where the gases from the kiln system are routed directly

to the raw mill to provide

the heat to dry the raw materials.

During operating

times when the raw mill is off (approximately

15% of the annual operating

time frame),

the gases bypass the raw mill and are routed directly

to the baghouse. Typically,

the Durkee Plant consumes

1,500,000

tons per year of raw materials

and has the capacity

to produce

1,000,000

tons of clinker annually. 2.2 Mercury Mercury is found in the environment

in one of the four following

forms: Elemental Hg (Hg °) "Liquid silver" or Hg vapor Inorganic Hg (oxidized) Mercuric compounds

Hg 2+ (e.g., HgS, HgCl_•, HgO, HgSO4) Mercurous compounds

Hg •-+ (e.g., Hg2CI2) Organic Hg Methylmercury

species

CH3Hg or MeHg Particulate-bound Hg- HgpAll four of these forms of Hg can exist in the environment.

Elemental,

inorganic,

and Hgp
are the types that are emitted

from the cement-manufacturing process.

Organic

Hg is not emitted from the cement-manufacturing process

because

organic

Hg is thermodynamically

precluded from forming. The form of Hg emitted dictates

the way in which the Hg will behave in the environment. Mercury that is emitted

from a cement kiln stack is deposited

in the local environment

or is lost to the global Hg cycle. Elemental

Hg is not water-soluble

and, upon being emitted,

has a residence time in the atmosphere

of 6 months

to 2 years. During this time, Hg ° can travel thousands of miles before being deposited.

Oxidized

Hg, by contrast,

has a residence

time of days once emitted

to the atmosphere.

Oxidized

Hg is water-soluble

and has greater potential

to enter into rainfall and waterways.

Particle-bound

Hg, upon being emitted,

has a residence

time in the atmosphere

of between

hours and years, depending

on the size of the particle.

Inhalation

of atmospheric Hg species

is not a serious health hazard,

even at the highest

ambient

levels. Similarly, ingestion

of Hg ° does not pose a serious hazard. Some of the Hg that is deposited

into waterways is converted

to MeHg by biological

processes.

The small percentage

of the overall Hg emissions that is deposited

in wetlands

and converted

to MeHg is the Hg that is focused

on from
an ecological

and human health perspective.

Recent studies in Clear Lake, California,

have indicated that Hgtotat levels in waterways

may not impact MeHg levels. The Oregon

Department of Environmental

Quality

(ODEQ)

has estimated

that, in the western

portion

of Oregon, approximately 83% of all Hg being deposited

from air originating

in Asia. 2.3 Previous

Mercury

Studies

for Cement

Kilns Only limited data are available

relating

to Hg emissions

from cement kilns. Equilibrium calculations suggest that HgCI2 is the dominant

Hg species in the flue gases from cement kilns at <480°-590°C. 2 Flue gas Hg speciation

measurements

and kinetic calculations

indicate

that Hg ° chlorination reactions

generally

do not attain equilibrium

because

of gas quench rates. Schreiber et al. 3 reviewed

the results from previous

Hg mass balance

studies and comprehensive

stack Hg measurement results on cement kiln systems

and concluded

that cement kiln systems

inherently control stack Hg emissions

to varying degrees.

Likely hosts for Hg in cement kilns are threefold: 1) cement kiln dust, 2) raw materials

in the in-line raw mills, and 3) cement clinker) Schreiber et al. 3 also describes

how levels in Hg emissions

could change as a result of the
raw mill operating

or not operating.

Data collected

during the SSBH testing indicates

a higher Hg emission

level with the raw mill not operating

as compared

to that with the mill in operation. One hypothesis

given for this release of Hg when the raw mill is shut off and bypassed

is explained by the fact that the in-line raw mill has the capability

to capture Hg when the raw mill is online. This Hg capture is possible

because

when the raw mill is online, the kiln gas containing volatilized Hg is used to dry raw materials

and sweep the mill of the finely ground and dr3, raw kiln feed material.

Because

the mill temperature

operates

at 90°-120°C,

the fine feed particles Hope. B.: Science of the Total En,,ironment.

2006. p 356. Senior. C.: Sarotim. A.: Eddings. E. Beha,,ior and Measurement

of Mercur? in Cement Kilns. Presented

at the 2(/03 IEEE-IAS/PCA

Cement Industry Technical

Conference.

Dallas. TX. May 4-9, 2003. Schreiber. R.J.. Jr.: Kellett. C.D.: Joshi. N. h•here,•g ,.•Iercucv Cont,o!s •,Vighii,• t/ze P,•,t/a•zd Ceme•,• Kiln R&D Serial No. 2841, Portland Cement Association.

Skokie. [L. 2005: pp 24.can

absorb Hg from the gas stream as the Hg condenses

on them. This Hg is then stored in the kiln feed silos, which supply the feed into the kiln system,

thereby reintroducing

the Hg, which will again volatilize

in the higher-temperature

zones of the pyroprocess.

When the raw mill is shut off, the Hg that has built up in the system through

this process

is no longer captured

in the
raw mill, but instead travels through

the facility's

APCD and out the stack, causing

increased levels of Hg. Mercury control

for cement

kilns has not been extensively

studied.

As the U.S. Environmental Protection

Agency

(EPA) determined

in trying to evaluate

the availability

of Hg controls for the portland

cement

National

Emission

Standards

for Hazardous

Air Pollutants (NESHAP), cement

plants have not installed

controls

for Hg emissions.

EPA has stated air pollution control

devices

(APCDs)

such as wet scrubbers

may provide

Hg control

as an unintended benefit,

but the level of Hg control has not been adequately

studied.

EPA recently required the few cement kilns with wet scrubbers

to perform

inlet and outlet Hg sampling

so as to identify

Hg control efficiency.

Those data have not been collected

and assessed.

Even when those data are collected

and available,

there will be significant

questions

as to the transferability of results from one cement plant to another

given the variability

in relative

proportion

of Hg forms encountered

in different

parts of the country. 2.4 Mercury

Control

Strategy Ash Grove has recognized

the concerns

regarding

Hg emissions

at its Durkee facility and has voluntarily

collaborated

with the Oregon

DEQ to investigate

commercially

viable solutions to the issue. In mid-2006,

Ash Grove was supplied

with data suggesting

that the process

Hg emissions were greater than previously

thought.

As noted above, the data concerning

cement kiln Hg emissions

are limited,

and data collected

at one cement

plant may not be relevant

to emissions from another

cement plant. Therefore,

in order to better quantify

its emissions,

Ash Grove engaged

in extensive

Hg testing in September

and December

2006. This testing generated detailed information

about the form, quantity,

and variability

of Hg emissions

from the Durkee facility. Based on these data, Ash Grove contracted

with the EERC to evaluate

potential

Hg control strategies

for the Durkee cement plant. The EERC is a nonprofit

branch of the University of North Dakota and is a national

leader in the research,

development,

and commercialization

of air pollution

control and emission-monitoring equipment.

Ash Grove is unaware

of any cement plant having installed

controls

specifically

to control

Hg. Therefore,

the EERC's

extensive experience developing

Hg controls

for the coal-fired

electric

utility industry

made it uniquely qualified to assist Ash Grove in this innovative

control technology

project. The EERC's

evaluation

of potential

Hg controls

identified

PAC injection

as the most promising technology

for controlling

Hg from cement plants. PAC injection,

fixed-bed

carbon, and wet scrubbing

have all been identified

as potential

Hg control technologies

for cement kilns. The scarcity

of water in the Durkee Plant vicinity

and the limited efficacy

of wet scrubbing

for controlling H• °• make it an inferior

control method.

Therefore,

this study was focused

on the feasibility and optimization

of PAC injection

for cement kilns. A secondary

study was performed
on fixed-bed

carbon, but this technology

was not more comprehensively

studied because

it has not been employed

in comparable

installations.

4The utilization

of a PAC injection

system at the Durkee Plant would require the installation of a new FF baghouse.

PAC is typically

injected

upstream

of a particulate

APCD. In the case of a cement facility,

an additional

APCD is needed downstream

of the existing

particulate

APCD. The Durkee facility recycles

the raw material

collected

in their primary

particulate

APCD, thus eliminating waste and enhancing

the efficiency

of the process.

At Ash Grove's

Durkee Plant, the particulate APCD is a FF baghouse.

Injecting

PAC upstream

of the existing

FF baghouse

would eliminate the ability to recycle baghouse

dust, resulting

in large amounts

of waste and lower process efficiency.

By injecting

PAC downstream

of the existing

FF baghouse

and capturing

that PAC in a secondary

FF baghouse,

the plant would be able to continue

recycling

of the baghouse dust collected

in the existing

primary

baghouse. The EERC designed

this project in order to better understand

the site-specific

control characteristics of the Durkee Plant. The efficiency

of a PAC injection

installation

is expected

to vary with the relative proportions

of Hg forms in a particular

gas stream as well as the proportion of naturally

occurring

oxidizing

agents such as chlorine.

Control

efficiency

is also expected

to vary as the Hg levels vary over time. In order to test these hypotheses

and draw meaningful conclusions as to the level of Hg control

that can be anticipated

from a PAC injection installation, the EERC installed

a temporary

PAC injection

system on a slipstream

from the Durkee stack, downstream

of the existing

particulate

APCD.

Inlet and outlet emissions

were studied over the course of approximately

4 weeks, during which time the types and amounts

of PAC were varied. This pilot study provides

a basis for predictions

as to the anticipated

control level that can be achieved

and the design parameters

for consideration

in engineering

a full-scale installation. However,

it is important

to note that this pilot system did not operate understeadystate conditions

for an extended

period and that the performance

documented

during this testing may or may not be sustained

during long-term,

full-scale

operation.
3.0 PROJECT

OVERVIEW 3.1 Goals and Objectives The overall goal of this project was to use a small-scale

mobile FF baghouse

operating

in series with an existing

Durkee baghouse

to perform

parametric

testing on a slipstream

of actual flue gas from Ash Grove's

Durkee

cement

facility to gain an understanding

of how various operating and design parameters

are likely to impact Hg control at the full scale. The Hg control strategies under consideration

involved

injection

of various

sorbents

into the second baghouse operating in series with the existing

particulate

control device. 3.2 ApproachAVork

Plan The EERC was on-site at the Durkee facility from April 10 to May 16, 2007. Appendix

A contains the resumes

of all EERC personnel

who participated

in this project.

Appendix

B contains the sample calculations

used during testing and the analysis

of the data collected. Appendix C contains

a daily description

of the testing performed

at the Durkee

facility. Appendix D desctibes

the quality assurance/quality

control procedures.4.0

FACILITIES

AND EQUIPMENT

DESCRIPTION 4.1 Description

of Ash Grove Durkee

Facility 4.1.1 Raw Material

Handling Three of the four raw materials

are found on-site in the Durkee quarry: limestone,

shale, and clay. Iron slag is the only imported

raw material

for the cement

process.

Iron slag is imported from off-site

sources,

unloaded,

and utilized

as a feed stream supplement.

Raw materials are withdrawn

from storage silos in proportioned

amounts

and conveyed

to the raw mill system. 4.1.2 Raw Mill The raw mill grinds and dries the raw materials

to raw meal. The mill is referred

to as an "in-line" raw mill because

it utilizes exhaust

gases from the pyroprocess

to dry and separate

the
raw meal. The raw mill operates

approximately

85% of the time the kiln operates

on an annual basis. The raw meal is combined

with recycled

material

from the main baghouse

to make kiln feed, which is stored in silos. The raw mill is shut off once a week for scheduled

routine maintenance. Typically,

maintenance

can be performed

over an 8- to 12-hour

period. The kiln typically continues

in operation

while the raw mill is off, utilizing

kiln feed stored in the silos. 4.1.3 Fuel Systems The plant has the capability

to use coal, natural gas, used oil, and tire-derived

fuel (TDF) to provide the energy required

for the processing

of the kiln feed in the pyroprocess.

Fuels are delivered to the multichannel

burner pipe in the kiln, to the in-line calciner,

and to theseparateline calciner

(SLC). During the time that this test was performed,

coal and TDF were the only fuels combusted. 4.1.4

The Pyroprocess The heart of the plant is a pyroprocess

with a kiln and two preheater/precalciner strings;
one string is referred

to as the in-line calciner

(ILC) string and the other as the SLC string. In this system, combustion

offgases

from the kiln and dual-string

preheater

are utilized

for drying and separation of fine raw material

in the in-line raw mill. Within the precalciner

system,

cool raw materials entering

the top stages of the preheater

tower mix with hot combustion

gases from the kiln and calciners.

The resulting

heat transfer

increases

the temperature

of the raw meal as it proceeds down the preheater

tower. When the raw meal temperature

reaches

approximately 1650°F, calcination

begins liberating

carbon dioxide

(CO,_) from limestone

(calcium

carbonate [CaCO3]), resulting

in the formation

of lime (CaO), which reacts with alumina,

silica, and iron in the kiln to make clinker.

Clinker

nodules

are gray pea- to walnut-sized

nodules

that contain

the minerals that, when ground with gypsum,

other additives,

and reacted with water, give concrete its strength.

The design of the preheater/precalciner system results in highly calcined

material reaching the rotary kiln; thus the kiln length is shortened

(versus a conventional

dry processkiln),

and less residence

time is needed for clinkering.

Consequently,

preheater/precalciner kilns
are shorter and more fuel-efficient

than conventional

wet and long-dry

process kilns. 4.1.5 Cement

Mill The facility operates

two cement mill systems

that grind the clinker with gypsum

and other additives to a fine powder to produce

the various types of cement. 4.1.6 Cement

Storage

and Shipping Finished cement is stored in silos or a dome prior to being loaded into tracks or railcars for distribution. 4.1.7 Description

of the Main Air Pollution

Control

Device The exhaust

gases from the pyroprocess

and in-line raw mill pass through

a conditioning tower and baghouse

system that control emissions

of particulate

matter. The baghouse

is a reverse-air design. This design isolates one compartment

of bag filters from the gas stream and utilizes process gases to dislodge

collected

particulate

matter from the interior of the filter media. The particulate

matter loosened

from the bags falls into collection

hoppers,

and screw conveyors remove the material

for recycling

to the process via the kiln feed silos. The dedusted

gases are discharged

to the atmosphere

through

the plant's main stack. The stack height is 295 feet. Test ports are available

in. the main stack at a height of approximately 230 feet. 4.2 Description

of the EERC Slipstream

Baghouse Shown in Figure 2 is the EERC's

trailer-mounted

baghouse

that was transported

to the Durkee cement facility and connected

in a slipstream

fashion to enable the testing on "real" flue gases under actual operating

conditions.

The slipstream

baghouse

(SSBH)

chamber accommodates twelve 6-inch FFs, with bag lengths up to 12 feet. This equates to approximately 226 ft 2 of filtration

area. To connect

the SSBH to the flue gas of the plant, two separate

10-inch flanges were required:

one at the exit of the cement facility's

FF and the other downstream

of this location.

The plant provided

these connections.•gn•a-"ouse Exit

Duct EERC BP30305. CDR Stack

•SBH

Figure 2. SSBH, trailer, and control room.

A variable-speed

fan is used to draw between

450 and 2700 actual cubic foot per minute (acfm) of flue gas (•300°F)

through

the slipstream

device to vary FF face velocity

between

2 and 12 ft/min. The fan speed is controlled

at a rate sufficient

to draw gases at or near the maximum system flow of 2700 acfm for all test conditions.

In comparison

to the full-scale

unit, the SSBH would be treating

only approximately

1.0%-1.1%

of the total facility's

flue gas. An 8-inch baghouse bypass line was utilized as a flow control mechanism.

Flow control was provided

by an orifice meter on the baghouse

effluent

stream, with a flow control valve inserted

in the 8-inch bypass line. Utilization

of the bypass line enabled

a constant

draw of flue gas and isokinetic

flow at the inlet nozzle for all test conditions.

In addition,

pipe velocities

were maintained

near 75 ft/sec for all test conditions,

preventing

dropout

of particulate

matter. The baghouse

chamber utilized between

one and three inlet ports (5-inch diameter),

depending

on test conditions.

Gases
were drawn from an 8-inch header at the baghouse

inlet. The baghouse

chamber

and inlet piping
were insulated,

with heat-traced

lines used to maintain

temperatures

above a specified

minimum, assumed to be 280°F. The following

was provided

for testing purposes: Access to the Durkee cement facility Assistance and cooperation

from plant personnel

during planning

and while on-site Assistance from plant personnel

to adjust valve positions,

if required,

and change out SSBH catch collection

barrels between

tests

8site location

with level grade to place trailer and mobile unit A 10-inch duct connected

after the facility's

baghouse

(SSBH inlet)
A 10-inch return duct connected

at the base of the stack (SSBH outlet)
An adequate

source of low-voltage

(480-V)

3-phase electricity

(=60 amp) Approximately 120 amp of 3-phase

(120-V)

electricity
An adequate

source of compressed

air (3/8- to l/2-inch

line) Approximately week was used to install and shake down the slipstream

equipment

before testing was initiated.

Several

operating

parameters,

such as gas flow, air to cloth (A/C) ratio, injection rate, etc., were varied during shakedown

testing. 4.3 Mercury

Monitoring 4.3.1 Main Stack Mercury

Monitor Mercury monitoring

was performed

at the main stack using a Tekran Model 3300 atomic fluorescence-based Hg vapor analyzer.

The mercury

monitor

(MM) was used in conjunction

with
a Tekran dry pretreatment/conversion unit to rapidly monitor

Hg ° and Hgtota• concentrations. Samples of flue gas were extracted

from the main stack and drawn through

an inertial gas separation (IGS) filter to remove particulate

matter. The IGS filter consists

of a heated stainless steel tube lined with sintered

material. The Tekran

instrument,

which was located

230 feet above ground along the main kiln stack, traps the Hg vapor from the conditioned

sample onto a cartridge

containing

an ultrapure gold sorbent.

The amalgamated

Hg is then thermally

desorbed

and detected

using atomic fluorescence spectrometry.

A dual-cartridge

design enables

alternate

sampling

and desorption, resulting in a nearly continuous

measurement

of the sample

stream.

An automatic

Hg ° permeation source was used to calibrate

the instrument

daily. Manual

Hg ° injection

calibration
on both cartridges

was also performed

for verification.

The Tekran instrument

measures

either Hgtotal or Hg °, with an analysis

occurring

approximately

every 2.5 minutes.

To prevent

the saturation of the unit's conditioner,

the flue gas stream was diluted at a ratio of 180:1. At this dilution rate, the system could measure

concentrations

exceeding

20,000 btg/m 3. 4.3.2 Slipstream

Fabric Filter Baghouse

Mercury

Monitor Mercury measurements

were made at the slipstream

FF baghouse

inlet and outlet using a Horiba/Nippon Instruments

Corporation

DM-6B.

The DM-6B

uses dual individual

channel atomic absorption

spectroscopy

to measure

Hg ° and Hgto•at concurrently

every 10 seconds.

The DM-6B uses a dry thermal

catalytic

pretreatment/conversion system

to transform

all Hg compounds to Hg ° for analysis

so that Hgtotal concentrations

can be determined.

A dilution system was also utilized

with the Horiba to prevent

saturation.

A dilution

ratio of 10:I allowedthis

system to measure

concentrations

above 10,000 btg/m 3. The Horiba MM is not considered

to be a robust system but is a very good research

tool. Figure 3 is a schematic

showing

the connection of the Horiba system to the SSBH.

ILl"

Main 8aghouse

Carbnn Baghouse Irlent'°n Height 26' Locatior

Inlet Samplin• 2750 acfm

EERC Mobile Slipstream Baghouse Ptpe

Trailer Footpnnt 48' 22" iVlair• Slack

Figure 3. Schematic

of the SSBH showing

the locations

of MM sampling

and carbon injection.
4.4 OH Method

Flue Gas Mercury

Measurements For verifying

the MM measurements

in the flue gas, ASTM International

(ASTM)

Method D6784-02 (Standard

Test Method

for Elemental,

Oxidized,

Particle-Bound,

and Total Mercury

in Flue Gas Generated

from Coal-Fired

Stationary

Sources

Ontario

Hydro Method)

was used. OH method samples

were withdrawn

from the flue gas stream isokinetically

through

a probe/filter system, maintained

at 120°C or the flue gas temperature,

whichever

was greater,

followed

by a series of impinger

solutions

in an ice bath. Particle-bound

Hg, Hgp, was collected

on a quartz 2+ filter in the front half of the sampling

train. Hg was collected

in impingers

containing

a chilled aqueous potassium

chloride

solution.

Hg ° was collected

in subsequent

impingers

(an impinger containing a chilled

aqueous

acidic solution

of hydrogen

peroxide

and three impingers containing chilled

aqueous

acidic solutions

of potassium

permanganate).

Samples

were recovered and analyzed

on-site by cold-vapor

atomic absorption

spectroscopy

(CVAAS)

using a CETAC M6000A

automated

Hg analyzer.

The OH method

samples

were typically

prepared

and analyzed the same day of collection

or the following

day.

104.5 Carbon

Trap (EPA Method

30B) Mercury

Measurements In addition

to using the OH reference

method,

the U.S. Environmental

Protection

Agency's (EPA's) draft reference

Method

30B (Determination

of Total Vapor-Phase

Mercury

Emissions from Coal-Fired

Combustion

Sources

Using Carbon Sorbent

Traps) was used. Proposed

Method 30B is a procedure

for measuring

Hgtota• emissions

from coal-fired

combustion

sources

using sorbent sampling

and an extractive

or thermal

analytical

technique.

The method

is intended

for flue gases that are not particulate-laden

(e.g., sampling

downstream

from particulate

control devices). 4.6 Powdered

Activated

Carbons The sorbents

used for this project were PACs obtained

from vendors

that had a product

on the market

readily

available

for use. Many experimental

carbons

do exist but were not considered for this project because

they are not widely available

commercially.

The selected activated carbons

were NORIT

DARCO

Hg and NORIT

e-1 I. The selected

treated activated carbons were NORIT

DARCO

Hg LH and Envergex

e-Sorb e-11. NORIT

DARCO

Hg is a multipurpose activated

carbon created from lignite coal. The NORIT

e-11 is a coarser version of the DARCO

product

line. A coarser

carbon was selected

to determine

if any significant differences, such as bag blinding,

could be found with the SSBH operation

with this product

over the more generic DARCO

Hg. The treated carbons

were both treated with a proprietary

process, adding the benefit

of increased

reaction

with the material

with the gas stream through halogenation. The carbons

chosen represent

the available

carbons

on the market today. Different carbon vendors

do exist, but their products

fall under the carbon types tested (halogen-treated and untreated).

Table

contains

information

about each carbon chosen for evaluation

in this study, including

a brief description

of the carbon material.

Table 1. Brief Description

of the Carbons

Tested During

Parametric

Testing Through the SSBH Carbon Name

Manufacturer

Availability Description DARCO Hg DARCO HgeDARCO Hg LH Envergex e-Sorb e-ll

NORIT Americas NORIT Americas NORIT Americas Envergex

Commercially available Commercially available Commercially available Readily available

Lignite coal-based Lignite coal-based,

larger particle size than DARCO

Hg Lignite coal-based,

halogentreated Proprietary treated carbon

4.7 Stack RATA Testing A relative accuracy

test audit (RATA)

was conducted

at the conclusion

of sorbent testing to aid in the identification

of the challenges

that would be encountered

in certifying

a MM for regulatory purposes.

Dates of testing are listed in Appendix

C. Sampling

at the stack with15

paired OH method

trains was conducted

over a 4-day period for the RATA. Analyses

of the OH method

trains were performed

on-site immediately

after being sampled.

The results of the paired OH method

samples

were then compared

to the averaged

stack MM data from the same time period. A traverse

was not conducted

before OH method

sampling

began. Examination

of previous testing performed

at the facility's

stack did not indicate

that stratification

of gas flow or stratification of Hg was occurring.

4 4.8 Fixed-Bed

Testing The EERC built a small fixed-bed

apparatus

with the capability

to provide

a slipstream

of flue gas to a fixed-bed

contactor

to investigate

this technology

for applicability

to this system as a Hg reduction

strategy.

The intent was to determine

the life of a typical granular

activated carbon when exposed

to the Durkee

process

gas. Several

attempts

were made at running

the apparatus. Because

of the low flow rate and limited time line of the project,

the apparatus

failed to achieve normal baseline

conditions

(no carbon in the bed) because

the metal in the system was absorbing Hg. Therefore,

no results were obtained,

and the carbon life was not determined.
5.0 RESULTS

AND DISCUSSION 5.1 Slipstream

Baghouse

Operation Mercury control testing occurred

across the SSBH over a 4-week period. During this time, the EERC evaluated

several parameters,

including

bag type, A/C ratio, activated

carbon type, activated carbon injection

rate, and baghouse

operation.

The first week of testing involved

a setup and shakedown

period of the SSBH; during this time, baseline

data were gathered

to evaluate the normal Hg concentrations

through

the baghouse

with a standard

polyphenylene sulfide (PPS) bag. Testing

then continued

with the evaluation

of several carbon types, which included treated and untreated

carbons. After results from parametric

testing with the four sorbents,

identified

in Table 1, were evaluated, comparative

results were analyzed

to determine

the best-performing

carbon,

which
was then used to conduct

the remaining

tests. This was done to control the number of variables

in the system when other parameters

such as differential

pressure,

bag type, and A/C ratio were evaluated. The remaining

baghouse

testing involved

the evaluation

of two other bag types, membrane and membrane/fiberglass, with varying

injection

rates and A/C ratios. Pressure change values were used in determining

the baghouse

operability

and bag type performance. During the injection

of PAC, the differential

pressure

was measured

to determine

if bag blinding was a concern.

After several injection

periods,

it was determined

that the differential pressure was not an issue for this test. The highest differential

pressure

that occurred

during testing with the PPS bags was l. 11 inches of water during the highest injection

rate of Envergex e-11. During injection

into the membrane

bags, the highest differential

pressure

was 0.04 inches of water. This is a very low differential

pressure,

but during the use of the membrane

bags, smalf
Cobb. G. Me*c',_Hv E••i,ssie)•zs

Te•t Rep()t-t: Prepared •or Ash Glt•e Cement C(•mpan?

Dec 5 through 8, 2006, _\irSource Technologies.

Inc., Sha•nee,

KS, 2(•06: p (•.
2quantities of fine carbon were determined

to have bled through

the bags. The highest differential pressures for the membrane/fiberglass bags was 2.42 inches of water. Appendix

C contains

the differential pressure

data in table form for all injection

periods. 5.2 SSBH Baseline

Testing Two days of baseline

testing occurred

on April 16 and 17, 2007. During these 2 days, baseline data were gathered

that demonstrated

the two main operating

cycles: raw mill on and
raw mill off. The primary

goal of collecting

baseline

data was to demonstrate

the typical Hg concentrations throughout

the SSBH system. 5.2.1 Raw-Mill-On

Baseline

Period Baseline results during the raw-mill-on

period were variable,

with an •.verage

daily Hg concentration at the inlet of the SSBH equal to 485 _+ 64 btg/Nm 3 and at the outlet equal to 461 _+ 79 btg/Nm 3 to one standard

deviation.

Since it was not expected

that the SSBH would remove Hg without the aid of a Hg control technology

(such as the injection

of PAC into the system),

the Hg removal efficiency

during baseline

conditions

(the native capture)

was expected

to be zero. This
means that the average

Hg concentrations

during a baseline

period should be the same at the inlet and outlet locations

of the SSBH. Based on the experience

of EERC and the statistical

evaluation presented in Appendix

G, it can be said that the native capture

is, in fact, zero and the Hg concentration at the inlet and the exit of the SSBH during the baseline

raw-mill-on

period are essentially the same. To compare

methods,

modified

carbon traps and OH method

sampling

were used in conjunction with the Horiba MM located at the inlet and outlet of the SSBH. These methods
were performed

as a set, with each method being performed

at both the inlet and outlet side of the SSBH. In order to allow a comparison

between

data collected

by the Horiba MM, carbon traps, and OH method

testing,

all three methods

were employed

during this baseline

period. The Horiba MM was collecting

and analyzing

samples

from the inlet and outlet of the SSBH. For approximately 15 minutes,

data were simultaneously

collected

at the inlet and the outlet via carbon traps. The difference

between

the carbon trap inlet and carbon trap outlet data is 12.2%, indicating good correlation.

Inlet MM data correlated

very closely with inlet carbon trap data. Outlet MM data differed

by 21.8% from outlet carbon trap data with the carbon trap appearing

to be biased high. For approximately

30 minutes,

data were simultaneously

collected

at the inlet and the outlet via the OH method.

The difference

between

the OH method

inlet and the OH method outlet data is 29.0%. The inlet OH method results indicate

a percent difference

of 28.6% from the MM average

at the inlet. This suggests

that there may have been an error with the inlet OH method

test as the inlet MM data correlates

well with the outlet MM data as well as the outlet OH method

data. The outlet MM monitor

data correlated

well with the outlet OH method data. Table 2 shows the results from this testing. Figure 4 shows the real-time

Hg monitor

data compared to carbon trap and OH method results.

13Table

2. Results

from Carbon

Trap and OH Method

Testing

During

Raw-Mill-On

Baseline Testing Test Method Test Method Test Inlet MM Hg

Hg

Inlet

Outlet MM Hg

Hg

Outlet

MM Method Concentration

Concentration

Difference

Concentration

Concentration

Difference

Difference ,tt g/N m3 %

bt g/N m3

%

% Carbon Trap 422

423

0.2%

384

478

21.8%

9.4% Ontario Hydro 512

384

28.6%

442

514

15.1%

14.7%

!41000 900- 8oo 700 600 5OO 4O0 300 2OO tO00 1000 900 800 700 600 500 400 300 200 1000

600 1 500 1 400 300 200 100 SSBH Inlet MM SSBH Outlet MM !•SSBH Inlet Carbon Trap •SSBH Outlet Carbon Trap •SSBH Inlet OH I•SSBH Outlet OH

'4/16/07 (1'0:30 24:00) SSBH Inlet MM SSBH Outlet MM I-I•SSBH Inlet Carbon Trap •SSBH Outlet Carbon Trap •-,,-SSBH Inlet OH •SSBH Outlet OH

0I) 4/16/07 (14:00 17:0

Figure 4. Raw-mill-on

baseline

results comparing

MM, carbon traps, and OH method.

155.2.2 Raw-Mill-Off

Baseline

Period On the second day of baseline

testing, the cement

facility's

in-line raw mill was shut off for planned

routine maintenance.

During this period, measurements

of typical raw-mill-off

Hg concentrations were obtained

through

the SSBH. The results of this testing indicated

an initial spike in the Hg concentration

for a brief period of time followed

by a period of Hg concentrations at a somewhat

steady state condition.

This level of Hg concentration

slowly decreased throughout

the testing period. The spike observed

during this raw-mill-off

condition reached Hg concentrations

close to 5000 btg/Nm 3 for a short period of time before stabilizing

to a concentration of approximately

2700 ,ug/Nm 3. The baseline

Hg concentration

at the inlet of the SSBH before the raw mill was shut off was 484 95 gg/Nm •, and the Hg concentration

at the outlet of the SSBH before the raw mill was shut off was 505 +_ 94 ,u,g/Nm 3. The average

rawmill-off baseline

Hg concentrations

for the inlet and outlet of the SSBH were 2570 _+ 260 #,g/Nm 3 and 2980 _+ 483 btg/Nm 3, respectively.

This yields a 14.8% difference

between

the inlet and outlet MM. Again, based on the statistical

analysis

of the native capture results and the experience of the EERC, we assume that these are essentially

the same, indicating

a zero native capture.During the raw-mill-off

baseline

testing, carbon traps were used and compared

with the MM. Three carbon trap tests were performed:

two at the inlet and one at the outlet of the baghouse. The results of carbon trap testing for the first set of traps indicate

a percent difference of 12.4% between

the carbon trap and MM data at the inlet of the SSBH and an 11.0% difference between carbon trap and MM data at the outlet of the SSBH. The difference

between

the inlet and outlet Hg concentrations

measured

by the MM at the SSBH during this set of traps indicated 34.8%, and because

of this, a second carbon trap test was performed

at the SSBH inlet. The results of this test yielded a percent difference

of 17.9% from the SSBH inlet MM to the inlet carbon trap, these results can be seen in Table 3. During this second test, the SSBH inlet MM agreed with the outlet MM with a percent difference

of 8.6%. These results can also be seen in Figure 5.cco

tO

to 5500 5000 4500 4000 3500 3000 2500 2000 1500 1000 5000 5500- 5000 2 4500 2 40001 35001 30002 25001 20002 15001 10001 5002 5508- 5000 4500 4000 3500 3000 2500 2000 1500 1000 5000 EERC J•30457 CDR SSBH Inlet MM SSBH Outlet MM :::-.• SSBH Inlet Carbon Trap1
• SSBH Outlet Carbon Trap
• SSBH Inlet Carbon Trap 2

4/17/2007 Time (0:00-24:00)

SSBH

Inlet MM SSBH Outlet MM z:7:= SSBH Inlet Carbon Trap1
• SSBH Outlet Carbon Trap
• SSBH Inlet Carbon Trap 2 4/17/2007 Time (6:00-8:30)

Figure 5. Raw-mill-off

baseline

results comparing

the MM to the carbon trap results.

17Table

3. Results

of Carbon

Trap Testing

During Raw-MilioOff

Baseline

Testing Test Method Outlet MM Test Method Test Inlet MM Hg

Hg

Inlet

Hg

Hg

Outlet Method Concentration

Concentration

Difference

Concentration

Concentration

Difference

MM Difference ,tt g/N m'

%

,u g/N m•

%

% Carbon Trap 2439

2762

12.4%

3468

3106

11.0%

34.8% Carbon Trap 3031

2533

17.9%

3302 8.6%
5.3 Parametric

Testing Four parameters

were tested during the pilot test: PAC type, PAC injection

rate, bag type and A/C ratio. Each of these parameters

were evaluated

during periods where the raw mill was operating so as to maintain

comparable

results.

This parametric

testing

resulted

in recommendations for use in designing

the full-scale

Hg control system. Parametric testing began on April 18, 2007, with the evaluation

of PAC type. DARCO

Hg
was the first PAC to be tested. Because

of the Hg concentrations

observed

in the system,

three injection rates (1, 3, and 5 lb/Macf)

were chosen for evaluation.

Before carbon injection

began, the Hg concentration

at the inlet of the SSBH was 594 _+ 70 gg/Nm 3, and the Hg concentration

at the outlet of the SSBH was 629 _+ 76 btg/Nm 3. The PAC injection

began with a feed rate of lb/Macf. When the feeder was turned on, the Hg concentration

at the outlet of the SSBH trended downward

quickly.

After a couple of hours of injection,

the outlet Hg concentration reached a steady state, or a period of time where the data appear to have leveled off during the injection testing, with an average

calculated

to be 136 _+ 45 btg/Nm •, a 73.4% reduction

in Hg. This average

is based on the data that correspond

to the time when the system reached

a steady state, as defined

above, during injection.

The percent removal

is based on the calculated

average Hg concentration

from the inlet MM compared

to the calculated

average

Hg concentration

from the outlet MM during the steady state condition. Results of this injection

test can be seen in Figure 6. Several

blanks in the data are observed during PAC injection

and SSBH recovery.

These blanks correspond

to times when MM maintenance (e.g., filter changes)

was occurring.

When injection

stopped,

the SSBH was cleaned and allowed

to return to baseline

conditions

before further testing was initiated.

The SSBH

t83500-. 3000- 2500- 2000- 1500 1000 500

1400 1200. 1000. 900 8oo700. 600. 500 400 3oo • 2oot
8O0

600 4 5oo400 300 200- O0 EERC JK30458 CDR Inlet MM o OutletMM Injection Period (1 Ib/Macf)

/ Injection Period

\' _/ (DARCO Hg- I•/•c0 ,I / •

•ag.o•se•olsin•

\

Expanded Injection Period, 4/18/2007

(8:00-16:00)
512 +_ 85

73.4 % Removal

136 + 45

Inlet MM

Outlet MM

Percent Removal 100 90 80 70 •E 60 50 oE 40 30 20 P 10 :• 0 Figure 6. PAC injection

results for the injection

of DARCO

Hg at lb/Macf.

tgrecovery

took longer than expected

based on what is typically

seen in a coal-fired

utility system. This was, in part, due to the relatively

clean (particulate-free)

gas stream seen in the cement facility versus a coal-fired

power plant system.

It was observed

that after the SSBH went through
a system-pulsing

sequence

for bag cleaning,

the Hg concentration

in the SSBH outlet gas dropped slightly.

One possible

reason this occurred

is that the pulse air created a situation

where mixing occurred

in the system, exposing

fresh carbon surface sites for the Hg to be adsorbed. The additional

two rates, 3 and 5 lb/Macf,

for the DARCO

Hg PAC were tested on the second day (April 19, 2007) of PAC injection

testing. Results showed

similar trends noted at an injection rate of lb/Macf

in that, upon the start of PAC injection,

the Hg concentrations decreased steadily

until a steady state was reached.

When the PAC injection

was increased

from 3 to 5 lb/Macf,

the Hg levels actually

increased

slightly,

but during this period, so did the inlet Hg concentrations.

As a method

for comparison,

a Hg removal

efficiency

is calculated

based on the inlet and outlet Hg concentrations

measured

at the time of injection.

For the two rates tested
on this day, the Hg removal

efficiencies

were 92.4% and 91.9% for 3 and 5 [b/MacE respectively. It appears

that no additional

benefit

is gained by increasing

the PAC injection above 3 lb/Macf.

The results from testing the additional

two rates for DARCO

Hg can be seen in Figure 7.

20o EERC JK30459 CDR Started Injection

• Inlet MM 3 Ib/Macf

• Outlet MM

Increased Injection to 5 Ib/Macf

• •letMMM•iecti°n

Te•'•°d'

4/19/2007

(10:40-15:01

Ib/Macf 800 700: 600: 500: 400- 300- 200- lOOo8O0 700 600 50O 400 3OO 2O0 •000

400- 300- 200- 100-0- Expanded

View 4/19/2007

(12:40-15:00) • DARCO Hg @ 3 Ib/Macf DARCO Hg @ 5 Ib/Macf •_ 553 _+ 37 --• 499 ÷ 29 •
°O

.•-

38el 45e10

120 110 100 •, o 90c80 ._o 70 ILl
0 50 E 40 r• 30 • 20 • I00
Figure 7. PAC injection

results for DARCO

Hg for the injection

of 3 and 5 lb/Macf.

21The

remaining

PAC injection

testing occurred

in the same manner as it did l-or the DARCO Hg injection

testing.

When testing for all PAC types and injection

rates was complete,

a Hg removal efficiency

curve was generated

in order to create a means of comparison

among the other carbon types. The Hg removal

efficiency

curves for all PACs tested are compared

in Figure 8. The results indicate

that each carbon tested performs

differently

in the SSBH system, with the untreated

carbons

performing

better than the treated carbons.
100 9O >:, 80 • 7O I.U 60

4o

• 2O100 EERC JK30455. CDR

DARCO Hg

0 2

3

4

5

6 PAC Injection

Rate, Ib/Macf Figure 8. PAC parametric

testing results performed

at an A/C ratio of 4 with standard

PPS bags.

One possible

explanation

for the untreated

carbon (DARCO

Hg) performing

better at this site takes into consideration

the carbon's

adsorption

capacity

and system reaction

time. Treated carbons (DARCO

Hg LH and Envergex)

have been shown to perform

better than untreated carbons in coal-fired

boilers,

especially

when reaction

times are short (electrostatic

precipitator [ESP] systems).

Thus the halogens

used to treat the carbon act like a catalyst,

oxidizing

the Hg in the system and allowing

for faster adsorption

onto the carbon. This is critical in systems

with higher SO,. concentrations,

because

SO• species have been shown to compete

for active sites on the carbon surface;

therefore,

the halogens

on the treated carbon allow the oxidized

Hg to bind to the carbon surface before the SO• species consume

the active sites. At the Durkee

facility,

in the SSBH, the SO,, concentrations

are very low compared

to a coal-fired utility system.

The high calcium

concentration

in the cement

manufacturing pyroprocess enables

the removal

of SOt species from the gas phase by forming

calcium

sultate. In cases such as this, the halogens

may still increase

reactivity,

but one would expect a decrease in sorbent adsorption

capacity

as the halogens

reduce the amount of active surface ,•rea available
on the carbon surface.

In addition,

it is reasonable

to assume that Hg ° would be physisorbed

onthe

surface

of the sorbent

along with NO> which could facilitate

oxidation

of the Hg and subsequent chemisorption

of the oxidized

species and, therefore,

removal

in the baghouse.

This is reflected

in the trends shown in Figure 8. At low injection

rates, the untreated

carbon performed

better because

of its additional sorbent capacity.

At the higher rate of 5 lb/Macf,

the treated carbons

appear to perform

as well as the untreated

carbons,

possibly

because

the large amount

of carbon injected

into the system provided for ample active surface

area, allowing

the halogens

to improve

reactivity

without jeopardizing active sites. However,

injection

of the treated carbons

at 5 lb/Macf

does not result in
a significant

difference

in Hg control efficiency

as compared

to untreated

carbon injected

at 3 lb/Macf.

There is no reason to choose halogenated

carbon over untreated

carbon, particularly

in light of potential

concerns

associated

with the use and disposal

of halogen-treated

materials. A small carbon particle

size was initially

thought to be a concern

because

of the possibility of bag blinding.

It was thought

that the fine particle size and small particle distribution

may blind the bags, causing

a high pressure

drop in the system.

Because

of this, a fourth carbon, DARCO Hg e-11, was tested that had larger particles

and a larger particle-size

distribution.

The injection of DARCO

Hg e-11 yielded a trend similar to the finer DARCO

Hg, but the Hg removal

results
were lower by 10%-15%.

This was most likely caused by the larger particle

sizes not having as much exposed

active surface area as the finer carbon. At the start of testing, a baseline

A/C ratio of 4 was chosen because,

at the time of the sorbent injection

parametric

testing, an optimal

A/C ratio was unknown.

Typically,

in acoalfired utility that has carbon injection

into a baghouse,

the A/C ratio is chosen to be anywhere between 4 and 8. Because

of the fine-particle

baghouse-blinding

concern,

a lower A/C ratio of 4 was chosen for the initial evaluation

of sorbent

effectiveness.

Based on the evaluation

of the results presented

in Figure 8, the DARCO

Hg carbon was chosen as the best-performing

carbon tested which, in turn, was then used to evaluate

the remaining

parameters. Once the PAC-type

parametric

testing was complete,

bag type and A/C ratio parametric testing began. The tests were conducted

in a similar manner as the PAC-type

evaluation

testing. The results from testing the three different

bag types suggest

that at PAC injection

rates of 3 lb/Macf

or higher the bag type does not play a role in Hg removal.

Shown in Figure 9 is a comparison of the three bag types at an A/C ratio of 4. It can be seen that at 3 lb/Macf

of PAC, all three bag types perform

similarly

with the largest percent difference

being 10% when the PPS and membrane

bags are compared.

Based on the variability

discussed

previously

between

the inlet and the outlet MM measurements,

it is likely that the bags are performing

essentially

the same at these conditions.

A comparison

showing

the calculated

percent differences

of the three bag types can be seen in Table 4. Because

of the nature of the process,

operating

temperatures

in the bag filter area of the process

can vary as much as 120°F and can exceed 400°F. Based on information provided

by GE Energy,

the membrane/fiberglass bags were the only bags tested that can withstand

continuous

operating

temperatures

above 400°F. This is a similar material

to the bag material

currently

used in the facility's

main APCD. Therefore,

based on the results seen

23110- lOO• 90• 8oZ 7oZ 6oZ E 5oZ

r• 4o•

"• 3o• ¢) 20•o• EERC BP30311 COR

Membrane PPS Membrane/Fiberglass

0 2

3

4

5 PAC Injection

Rate, Ib/Macf Figure 9. Bag type comparison

showing

their effectiveness

with regard to Hg removal efficiencies.
in Table 4 and Figure 9, the membrane/fiberglass bags appear to be the preferred

bag choice as they performed

similarly

to the other two bags and are the only bag type that is recommended

for continuous operation

when experiencing

temperatures

above 400°F.
Table 4. Comparison

of Bag Type Results Mercury Removal

Efficiency,

% Bag Type

i lb/Macf

3 lb/Macf

5 lb/Macf PPS 73

93

92 Membrane 46

84

98 Percent Difference

45 %

10 %

6 % PPS 73

93

92 Membrane + Fiberglass

62

86

100 Percent Difference

16%

8%

8% Membrane 46

84

98 Membrane + Fiberglass

62

86

100 Percent Difference

30%

2%

2%

In order to evaluate

,•C ratios, DARCO

Hg was injected

at the same three PAC injection rates {1, 3, and 5 lb/Macf)

and at f'our A/C ratios (4, 6, 8, and I0). The results for the
24membrane/fiberglass bags indicated

that at the lowest injection

rate, lb/Macf,

the Hg removal efficiency increased

with increasing

A/C ratio. This could be caused by the greater flow rates causing more mixing in the system. These results can be seen in Figure 10. With this type of bag, it appears

that A/C ratios above 6 have little effect on the Hg removal

efficiency.

Mercury

110 100

2OI00 EERC BP303og. CDR

[]

0 2

4

6

8

10 Air-to-Cloth Ratio Figure 10. Membrane/fiberglass bags parametric

testing results showing

effects of varying A/C ratio. Tests at 5 lb/Macf

were not performed.
removal efficiencies

of approximately

90% were achieved

at A/C ratios of 6, 8, and 10 with PAC injection rates of 3 and 5 lb/Macf.

Figure 11 displays

the results with respect to PAC injection rate versus Hg removal

efficiency.

The results indicate

that injection

rates higher than 3 lb/Macf give insignificant

increases

in Hg removal

efficiencies

at an A/C ratio of 6. Similarly,

there is essentially no material

difference

in control efficiency

achieved

by increasing

the PAC injection rate above 3 lb/Macf.

Increased

PAC injection

rates raise concerns

regarding

greater solid waste generation rates, and so absent any material

increase

in control efficiency,

there is no reason to operate at a higher PAC injection

rate for a system designed

for an A/C ratio of 6.

25110-lOO . !90- 8oZ 70: 602 502 4o: 30:

0 EERC BP30310 CDR

2 3

4

5 PAC Injection

Rate, Ib/Macf Figure 11. Membrane/fiberglass bag parametric

testing results showing

effects of varying

PAC injection rate. During the testing of the membrane/fiberglass bags the injection

of DARCO

Hg was evaluated during a raw-mill-off

operating

period. This test was performed

in order to evaluate the achievable

Hg removal

efficiency

during an operation

period when the Hg concentrations
were elevated,

typical of raw-mill-off

conditions.

Four PAC injection

rates were evaluated:

1, 3, 5, and 10 lb/Macf.

The results indicated

that only moderate

Hg removals

(approximately

52% and 58%, respectively)

were achievable

with injection

rates of 3 and 5 lb/Macf.

Because

of this, the injection

rate was increased

to I0 lb/Macf

to gain an understanding

of the level of impact on Hg control efficiency.

The results at the injection

rate of 10 Ib/Macf

yielded

a Hg removal efficiency of 88%. Results for this testing are summarized

in Figure 12.

260 0 EERC JK30449. CDR 9O o• 80 z0 "• 60 so

a0 20 10 Membrane/Fiberglass

Bags / •Raw Mill Off with

0 2

4

6

8

10 PAC Injection

Rate, Ib/Macf Figure 12. Raw-mill-off

injection

testing with membrane/fiberglass bags at an A/C ratio of 8.
Carbon injection

at full scale prior to the main baghouse

was conducted

on three different days (April 26, May 3, and May 10) with the raw mill off, coinciding

with planned

routine maintenance. For purposes

of this test the Darco Hg LH carbon was utilized.

Injection

rates were changed

on each of the three days from 1, 3, and 5 lb/Macf.

The effect of carbon injection
was measured

with the Tekran MM located at the main stack. The result of full-scale

carbon injection is shown in Figure 13. A more significant

reduction

is seen with 5 versus 3 lb/Macf

due to the high Hg emission

levels during raw-mill-off

conditions

as compared

to the raw-mill-on conditions during the other parametric

testing. The difference

is significant

enough to suggest the higher injection

rate during this condition.

The level of Hg reduction

measured

was very similar with that of testing conducted

on the SSBH during raw-mill-off

conditions.

Using the average value between

the full-scale

and SSBH injection

tests at a rate of 5 lbfMacf

yields an approximation of the Hg removal

during raw mill off of 63%.

27O0 EERC JK30456 CDR 9O
• 80 •) 7O 6o

4o • 30 • 20]0

• Full-Scale

Raw-Mill-Off Injection of DARCO Hg LH

0 2

3

4

5 PAC Injection

Rate, Ib/Macf Figure 13. Full-scale

carbon injection

results.
Based on the parametric

testing,

the EERC recommends

that a full-scale installation should be designed

based on the following

parameters: Parameter PAC Type

Design Criteria Untreated carbon

Comments Untreated

PAC performs comparably tohalogentreated PAC, while avoiding potential environmental issues associated

with use of halogens. Bag Type

Fiberglass

with membrane

All bags performed comparably, but fiberglass with membrane

withstands higher temperatures. A/C Ratio

6to8 Lower A/C ratios resulted

in lower control efficiency. Increasing A/C ratio over this range results in higher energy consumption

without increased control efficiency.

Hg control

28Injection Rate

3 lb/Macf

(raw mill on) 5 lb/Macf

(raw mill off)

Elevated

PAC injection

rate during raw-mill-off conditions may not be necessary after first hour.
Based on the pilot-scale

testing, there is a reasonable

likelihood

that a full-scale

installation designed using these parameters

would be expected

to perform

as follows:

• Approximately

90% Hg control during raw-mill-on

conditions

(annual average).

• Approximately

60% Hg control during raw-mill-off

conditions

(annual average).

• A weighted

average

of approximately

77% control (annual average). Calculations used to determine

the above parameters

can be found in Appendix

H. 5.4 Stack Hg Measurement A Tekran Model 3300 MM was installed

in the main stack to measure

Hg ° and Hgto,al- This
was done with the intention

of determining

the potential

for future use as a continuous monitoring device rather than determining

the ability to certify the instrument

for compliance purposes. The MM located in the stack began logging

data on April 13, 2007. The instrument logged data 24 hours a day until May 13. One technician

was dedicated

to monitor

the operation of the instrument

each day. The typical day ran from 6:30 a.m. to the end of scheduled

testing, which varied from 4:00 p.m. to 6:00 p.m. Each day the zero and span of the analyzer

was checked along with the gas dilution

factor. All connections,

umbilical

temperature,

system pressure, and gas flow rate were also checked.

Daily spikes to the analyzer

and also the probe
were conducted

using a calibration

source. The previous

night's data were also reviewed

daily for any indications

of machine

malfunction. The mechanical

operation

of the analyzer

allows for a single data point to be logged approximately every 2.5 minutes.

The theoretical

number of data points that could be logged in a day would be 576. While calibration,

zero and span checks, and spiking are being performed,

the measurement of the gas stream is interrupted;

thus the theoretical

maximum

was never reached. On average,

505 _+ 24 data points at one standard

deviation

were logged per day, which is 88% of theoretical maximum. During April 15 through

17, a daily OH method

test and a draft method carbon trap were conducted to verify that the MM was measuring

Hg levels accurately.

A graphical

example

of the correlation

for April 15 is shown in Figure 14. Sampling

occurred

during raw-mill-on conditions. A numerical

comparison

for all 3 days is shown in Table 5. The correlation

was

295O0 450 400 350 300 250 200 150 100 5O0 4/15

4/15

4/15

4/15

4/15

4/15

4/15

4/15 4:00 6:00

8:00

10:00

12:00

14:00

16:00

18:00 Date/Time Figure 14. Graphical

comparison

of MM, carbon trap, and OH method for April 15, 2007.
Table 5. Comparison

of Sampling

Methods

Showing

Difference

of MM with Carbon Trap and OH Method

Date

Carbon MM, Trap, gg/Nm 3 ,ttg/Nm 3 MM to

MM to OH Trap to OH Carbon Trap Method

Method Absolute OH

Absolute

Absolute Difference, Method,

Difference,

Difference, % •g/m 3

%

% April 15

279

299

6.9

306

9.2

2.3 April 16

374

388

3.7

329

12.8

16.5 April 17

2046

2039

0.3

2460

18.4

18.7
sufficient enough

to allow the use of modified

carbon traps as a check for the stack Hg monitoring. The modified

carbon trap results are shown in Table 6. Appendix

E contains

daily plots of the MM data.

30Table 6. Stack Emission

Carbon

Trap Data Carbon Trap, Sample Date

MM, •ttg/Nm 3

•tg/Nm 3

Absolute Difference,

% 4/l 5/07 279 299 6.9 4/16/07 374 388 3.7 4/17/07 2046 2039 0.3 4/19/07 527 514 2.5 4/20/07 443 375 16.6 4/22/07 37 381 2.7 4/23/07 363 364 0.3 4/24/07 480 528 9.5 4/25/07 435 446 2.5 4/26/07 1375 1607 15.6 4/27/07 227 205 10.2 4/28/07 411 344 17.7 4/29/07 345 395 13.5 4/30/07 459 416 9.8 5/1/07 691 626 9.9 5/1/07 611 533 13.6 5/2/07 527 505 4.3 5/3/07 2570 2458 4.5 5/4/07 373 403 7.7 5/4/07 393 380 3.4 5/5/07 227 253 10.8 5/5/07 332 371 11.1 5/6/07 277 304 9.3 5/11/2007 154 148 4.0 5/11/2007 124 112 10.2

3!Mercury concentration

at the stack was observed

to be variable

on a daily, even an hourly, basis. Figure 15 shows graphs for the Hg•o•a• and Hg ° stack output for April 23 and May 1. The

1000 EERC BP30308 CDR 800 600 400 200 Total Hg Elemental Hg

2:00 4:00 6:00 8:00 10:00 12:00 14:00 16:00 18:00 20:00 22:00 April 23, 2007 1000" 0:00

0 800 600 400 20000:00 2:00 4:00 6:00 8:00 10:00 12:00 14:00 16:00 18:00 20:00 22:00 0:00 May 1,2007 Figure 15. Comparison

MM graphs for April 23 and May showing

the variability

of Hgtotal and Hg ° output. variability between

these 2 days is high. Also of note is that the ratio of Hg ° to Hgtotal is highly variable as welt. The analysis

of process

data collected

on these 2 days shows the pyroprocess and raw grinding

systems

were operated

under similar conditions.

Table 7 illustrates

the similarities. The data indicate

kiln and raw mill feed rates and kiln fuel rates are similar.

The daily average

of critical temperatures

in the system also shows that the temperature

profile of the pyroprocess and raw milling system on each of the 2 days were similar. Stack conditions

as well show that the gas flow, temperatures,

and oxygen

levels at that location

were similar over the 2 days.Table

7. Comparison

of Process

Data for April 23, 2007, and May 1, 2007 April 23, 2007

May l, 2007 Description Units

Average

Std. Dev.

Average

Std. Dev. Kiln Feed Rate Mtph

235

2.36

236

4.13 Stack Gas Flow Rate

Dry scfm

138,437

5812

144,595

78t5 Stack O•_ %

6.5

0.72

6.6

0.70 Stack Temperature °C

101

2.3

103

3.30 Main FF Inlet Temp. °C

111

9.00

117

12.70 ILC Stage 1E Exit Temp.

°C

392

5.90

397

5.20 ILC Stage 1W Exit Temp.

°C

408

7.40

415

7.60 SLC Stage Exit Temp.

°C

339

3.50

338

5.40 SLC Coal Feed Mtph

6.3

0.18

6.2

0.32 Kiln Coal Feed Mtph

7.2

0.32

7

0.28 TDF Feed Lb/hr

2000

NA

2000

Na Raw Mill Feed Mtph

200

NA

201

Na Raw Mill Exit Temp. °C

97

0.92

97

1.30 Raw Mill Motor Power

kWh

1007

41.30

989

46.60 Figure 15 helps to explain

the lack of comparability

of previous

OH method

tests conducted for Ash Grove. It is clear to see that two sampling

tests conducted

on even the same day will most certainly

not yield similar results. The variability

of past OH method

tests along with this day-to-day

variability

provides

an approximation

of the variability

of the Hg in the limestone from the on-site mine and its impact on emissions. To further illustrate

the variability,

Figure 16 charts the overall average

stack Hg output alongside the daily averages

of some selected

days for the period when the raw mill was on. Error bars display one standard

deviation

of the average

value. The average

raw-mill-on

value was 408 +_ 118 •g/Nm 3 for Hgtotal and 215 _+ 113 gg/Nm 3 for Hg °. During raw-mill-off

periods measured during the testing period, the average

value was 2254 + 981 •ug/Nm 3 for Hgtota• and 305 _+ 182 [tg/Nm • for Hg °. A weighted

average

combining

the relative

times of raw-mill-on with raw-mill-off

periods yielded an average

Hgtota• output of 685 + 408 •ug/Nm • and an average Hg ° output of 229 ___ 127 •tg/Nm •. The error for the weighted

averages

is calculated

using a pooled standard

deviation

based on the combined

data sets of raw mill on and raw mill off. Graphs of daily average

Hg concentration

at the main stack can be found in Appendix

F. A statistical discussion

of the variability

is given in Appendix

G.EERC BP30307. CDR 8OO 700 600 500 400 300 200 1000 L•

Hg [/Elemental Hg ]

Overall 14-Apr

23-Apr

25-Apr

-May

4-May Figure 16. Average

Hg concentration

during raw-mill-on

conditions

over the entire test period compared to various specific

days.
When the raw mill shuts off, the Hg emissions

increase.

Figure 17 shows the MM data during a typical raw-mill-off

period. The increase

is shown to affect the oxidized

portion much
more than the elemental

portion.

Oxidized

Hg levels rose over 400%, whereas

the elemental portion increased

by roughly

one-third.

Reaction

of the system to the mill outage was fairly quick, as the rise of Hg at the beginning

of the outage and the reduction

back to typical levels when the mill is turned back on occur within the span of approximately

30 minutes.

The increase in emission

during raw-mill-off

conditions

is discussed

in detail in Section 2.3.

346000
5OOO
4000
3000
20O0
1000
0 0:00 Total Hg Elemental Hg

4:00 8:00 12:00 16:00 20:00 0:00 4:00 8:00 12:00 16:00 20:00 0:00 April 15 through

16 Figure 17. Stack MM data of raw-mill-outage

overnight

April 15 through

16.
5.5 Analytical

Methods

and Procedures

Their Applicability

at the Durkee

Facility The temporary

installation

of the stack MM did not follow EPA Method

PS-12a for several reasons. PS-12a

is intended

to assess the MM performance

for minimum

maintenance requirements for a permanent

installation.

This project was intended

to attempt the measurement of the Hg levels at the Durkee facility under many conditions,

with the expectation

to evaluate the performance

of sorbent additions

and how they affect Hg reduction.

To achieve this, the MM was scrutinized

much more closely

than would be desired

or contemplated

for routine measurement. Further, the method

requires

the use of National

Institute

of Standards

and Technology (NIST)-traceable standards

for both Hg ° and Hg +. An elemental

source was used for calibration purposes. Oxidized

sources

are a new commodity,

and the EERC does not yet have access to them. None of these is NIST-traceable.

NIST-traceable

standards

for Hg simply do not yet exist. Parameters such as the maximum

potential

concentration

and high span were not determined because

of limited information

about the nature of the Hg levels at this facility. Stratification was not checked

but was deemed

not necessary

based on previous

testing conducted at Durkee.

Drift tests were not conducted

because

the systems

were being evaluated daily by a technician. It is important

to mention

that the operation

of the MM during this project was not simply plugging in the instrument

and turning it on. The Hg levels encountered

at this facility were much higher than intended

for routine MMs. The sampled

gas stream had to be diluted before the
35instrument conducted

its measurements

to prevent

saturation

of the detection

cells. Also, factors such as the difference

of the Hg output between

raw mill off and raw mill on, temperature changes in the room in which the instrument

was housed,

and inherent

instrument

drift required that a dedicated

technician

carefully

check the instrument

daily. The use of draft method

carbon traps as a replacement

for the modified

OH method worked very well at this facility.

Values obtained

were comparable

to the OH method and MM measurements. The benefits

of this method are that the training

and investment

to use the needed equipment are small, and the method

is easy to perform,

making

it inherently

more reliable

in a plant setting.

Analyses

of the samples

can be completed

in under an hour, so this method generates timely results. The exact length of time a trap can sample before being saturated

has not been determined.

However,

carbon traps provide

an excellent

means of routinely

checking Hg APCD performance. 5.6 Main Stack RATA Testing The Tekran MM installed

on the main stack did not pass a RATA.

A summary

of the results can be seen in Table 8. Only five of the 12 paired OH method

samples

were within the passing 20% difference

limits. Three additional

paired trains were conducted

and passed within limits. Even with the additional

three tests, the RATA failed, with only eight of the needed nine passing pairs. Agreement

between

the two OH method pairs was very good, but two of the pairs had to be thrown out because

they differed

by more than 10%.
Table 8. RATA Test Results OH Method

Probe OH Method OHMethodSide, Relative

OH Method

MM

to-MM RATA btg/m 3

Difference,

Value,

Value,

Difference, Run No.

A

B

%

gg/m 3 btg/m 3

%

Pass/Fail 5220 5397

1.7

4438

3673

18.9

Pass 2 351

312

5.9

276

467

53.2

Fail 3 410

395

1.9

337

516

42.0

Fail 4 191

220

7.1

170

540

104.2

Fail 5 379

349

4.1

305

324

6.0

Pass 6 393

338

7.5

306

315

2.9

Pass 7 474

408

7.5

369

328

11.8

Pass 8 933

797

7.9

732

766

4.5

Pass 9 6624

6519

0.8

5573

3318

50.7

Fail 10 6499

9431

18.4

6762

3632

60.2

Fail 11 6416

6805

2.9

5652

3775

39.8

Fail 12 577

460

11.3

430

459

6.5

Fail 13 449

390

7.0

349

366

4.8

Pass 14 394

348

6.2

311

342

9.5

Pass 15 359

335

3.5

294

286

2.8

Pass Noapproved method

exists to perform

a RATA for a MM operating

at Hg levels above 150 tt•/m 3. Concentrations

during the testing were 2 to 45 times that level. When measuring

at
36these

levels, both the MM analyzer

and the reference

method lab bench analyzer

require that the sample undergo

significant

dilutions.

This increases

the opportunity

for significant

error. If a MM is ever intended

to be permanently

installed

at the Durkee facility and be required

to pass a RATA, then a procedure

would need to be written. 5.7 Fixed-Bed

Testing The work at Durkee to evaluate

the fixed-bed

option for Hg control was not successful,

as stated earlier in Section 4.8. The EERC is, however,

involved

in ongoing

research

evaluating

fixed beds for use in removing Hg for process

gas streams.

The results to date indicate

that it is possible

to capture a high level of Hg while maintaining

a low differential

pressure

through

the fixed bed, but several parameters are unknown

and are site-specific.

The main unknown

at this time is the carbon life. Several gas components

can potentially

lead to decreased

carbon life and are currently

being evaluated. The technology

itself has not gone through

the rigorous

testing that PAC injection

into APCDs has. As a result, EERC cannot recommend

the technology

at this time.
6.0 CONCLUSIONS 6.1 SSBH Testing The EERC performed

extensive

SSBH testing at Ash Grove's

Durkee Plant from April 17, 2007, through

May 8, 2007. The main focus of the SSBH testing was to evaluate

whether

the injection of PAC into a secondary

baghouse

is a viable option for Hg removal

from the Durkee facility and what design parameters

should be utilized

in order to design a robust,highperformance control installation.

Significant

variability

was identified

in Hg mass and form at the SSBH inlet. Nonetheless,

by comparing

inlet Hg concentrations

to outlet Hg concentrations, the EERC was able to identify

clear design choices

for a full-scale

Hg control

installation appropriate for the Durkee cement kiln. The following

parameters

were tested during the pilot project:

PAC type, FF bag type, A/C ratio, and PAC injection

rate. Based on this testing, the EERC is able to make recommendations
as to the predicted

optimal

design and operating

parameters

for the full-scale

PAC injection installation. PAC Type: Results indicated

that for the variety of PACs tested (halogen-treated

and untreated), the untreated

carbon, DARCO

Hg, performed

as well or better than the halogen-treated

carbons. Use of the untreated

carbon avoids the potential

for secondary

environmental

impacts

associated with the use of halogenated

products.

Therefore,

the untreated

carbon, DARCO

Hg, was chosen to evaluate

the other parameters. Bag Type: Of the three bags tested (PPS, membrane,

and membrane/fiberglass), all three performed well. However,

dust found downstream

of the membrane

bags indicated

that a small amount of PAC was able to penetrate

the bags. As this could lead to higher particulate

loading in

37the

main stack exhaust

gas, the membrane

bags were dropped

from consideration.

The fiberglass with membrane

bags are rated for a maximum

continuous

operating

temperature

of 500°F, while the PPS bags are only rated for a maximum

continuous

operating

temperature

of 375°F. Because of concerns

over bag failure due to elevated

temperatures

as a result of process

upsets, the fiberglass with membrane

bags were identified

as the best bags for use in a full-scale

system. A/C Ratio: Four A/C ratios were evaluated:

4, 6, 8, and i0. The one common

trend existing between testing the A/C ratios with the three different

bags was that when the A/C ratio was increased, the Hg removal

efficiency

also increased.

However,

the results indicated

that an A/C ratio greater than between

6 and 8 did not provide

a material

additional

benefit in terms of Hg removal efficiency.

Performance

was not significantly

different

between

the 6 and 8 A/C ratios, and so the choice of A/C ratio within this range should be left to the FF baghouse

manufacturer. In summary,

the EERC recommends

that the secondary

baghouse

serving

the full-scale

PAC injection installation

be designed

with an A/C ratio of between

6 and 8. PAC Injection

Rate: Three PAC injection

rates were evaluated

during raw-mill-on

conditions:

1, 3, and 5 lb/Macf.

The data showed

that at an A/C ratio of between

6 and 8, there is not a significant additional

Hg removal

efficiency

gained by increasing

the injection

rate above 3 lb/Macf during raw-mill-on

conditions.

Testing

was performed

during raw-mill-off

conditions using four PAC injection

rates: I, 3, 5, and 10 lb/Macf.

These tests showed

that Hg control increased with increased

PAC injection.

The highest control efficiencies

were reached

during the time when 10 lb/Macf

were injected.

Based on the expense

and system wear of injecting

at a rate of 10 lb/Macf

and the uncertainty

whether

a baghouse

system would maintain

the control levels seen in the short term injection

test, an increased

injection

rate of 5 lb/Macf

during raw-mill-off conditions is warranted.

Therefore,

we recommend

that the full-scale

installation

be designed

for a PAC injection

rate of 3 lb/Macf

during raw-mill-on

conditions

and 5 lb/Macf

duringraw-milloff conditions.

As testing suggested

that the highest Hg emissions

occur during approximately the first hour of a raw-mill-off

period, the elevated

PAC injection

rate may not be necessary

for the full duration

of the raw-mill-off

event. Control Efficiency

and Optimization

Period: The results gathered

from testing the SSBH are only an indication

of the relative differences

between

the different

parameters

tested. While the data indicate

that a 90% Hg control efficiency

can be reached

on a long-term

average

basis during raw-mill-on

conditions,

we caution Ash Grove against assuming

that the SSBH results will match the performance

on the full-scale

unit, particularly

in the first 12 to 18 months

of operation. It is our expectation

that a PAC injection

unit designed

and operated

consistent

with the parameter

choices

outlined

above has a reasonable

likelihood

of reaching

the 90% control level on an annual average

basis during raw-mill-on

conditions.

Likewise,

it is our expectation that that a PAC injection

unit designed

and operated

consistent

with the parameter

choices outlined above has a reasonable

likelihood

of reaching

a 77% Hg control level on an annual average and mass-weighted

basis. However,

the differences

between

what occurs when controlling 1% of the exhaust

gas over short periods and controlling

100% of the exhaust

over long periods

could result in a lower control efficiency.

In addition,

our experience

suggests

that Ash Grove will require at least 12 and more likely 18 months to optimize

a t'ull-scale

installation ,,,,here, as here, the installation

would be the first of its kind in the industry.

At the end of that

38period,

Ash Grove should have adequate

data to determine

whether

a 77% weighted

control efficiency (annual average)

is a realistic

target. 6.2 Performance

Monitoring In order to demonstrate

the performance

of a PAC injection

system, Ash Grove will need to implement

some sort of periodic

Hg-monitoring

program.

Such programs

can rely upon continuous monitoring

or periodic

monitoring.

Although

two types of continuous

MMs were used during this study, neither of these monitor

types, nor any other that we are aware of, is robust enough

to withstand

a cement

kiln stack environment

nor analyzes

Hg at the concentrations found in the Durkee exhaust

gases. Each MM used in the pilot study required

a dedicated technician.

Such an allocation

of resources

is simply not realistic

in an operating

plant. In addition,

there is no approved

method

for performing

a RATA should a continuous

MM be installed on the Durkee

main stack. Therefore,

at this time, we do not recommend

the use of continuous MMs for monitoring

the performance

of the PAC injection

installation. The EERC recommends

that carbon sorbent traps would be the best method

to allow Ash Grove to monitor

Hg emissions

at the Durkee

facility.

Carbon

sorbent traps present

numerous advantages over MMs in the workplace,

including

their inherent

reliability.

Results

from carbon sorbent traps compared

favorably

with results obtained

from OH method

testing and the MMs during the pilot study. The periodic

testing of Hg emissions

using carbon sorbent

traps will enable Ash Grove to confirm

the performance

of the PAC injection

installation

while avoiding the significant

issues currently

posed by MMs. 6.3 Fixed-Bed

Option The work at Durkee

to evaluate

the fixed-bed

option for Hg control was not successful because of problems

with the test equipment.

Although

fixed-bed

technologies

appropriate

for cement kiln exhaust

gases may be developed

in the future, the current

lack of system performance data make it difficult

at best to design a full-scale

fixed-bed

system for use at Durkee. Based on the research

to date, the EERC cannot recommend

the fixed-bed

technology for application

at the Durkee Plant.

39APPENDIX A PERSONNEL RESUMESTable A-1. List of Personnel

and Task Responsibilities Person Project Task Michael Jones John Kay Brandon Pavlish Richard Schulz Jay Gunderson Kirk Williams Robert Jensen Brace Dockter Don Toman William Wilson Kyle Martin Eric Zacher Steve Sollom Ray DeWall Ray Johnson Scott Schulz Dave Westerman Bill Gerszewski Ken Jerik Project Manager Field Manager Field Manager Sampling Manager SSBH Operator SSBH Operator/Sorbent

Injection SSBH Operator/Sorbent

Injection Sorbent Injection MM Operator MM Operator MM Operator MM Operator/Chemist Chemist Chemist Sampler (no resume available) Sampler (no resume available Sampler Sampler (no resume available Sampler (no resume available

A-IDR. MICHAEL

L. JONES Senior Research

Advisor Energy & Environmental

Research

Center (EERC),

University

of North Dakota (UND) 15 North 23rd Street, Stop 9018, Grand Forks, ND 58202-9018

USA Phone (701 777-5000,

Fax (701 777-5181,

E-Mail:

mjones @ undeerc.org Principal Areas of Expertise Dr. Jones' principal

areas of interest

and expertise

include

management

of and technical direction for multidisciplinary

science and engineering

research

teams focused

on a wide range of integrated

energy and environmental

technologies.

Specific

program

areas of interest include clean and efficient

combustion

of low-rank

fuels, matching

of fuel characteristics

to system design and operating

parameters,

development

of advanced

power systems

based on low-rank fuels, fundamentals

of combustion

and gasification,

ash deposition

in combustion

and gasification systems,

and analysis

of inorganic

materials.

Projects

emphasize

a cradle-to-grave approach from resource

assessment,

to optimum

utilization

systems,

to minimization

of emissions and waste management

featuring

by-product

utilization. Qualifications Ph.D., Physics,

University

of North Dakota,

1978. M.S., Physics,

University

of North Dakota,

1973. B.S., Physics,

Bemidji

State University

(Minnesota),

1971. Professional Experience 2004-Present: Senior Research

Advisor,

Energy

& Environmental

Research

Center (EERC), University of North Dakota

(UND),

Grand Forks, ND. Dr. Jones' responsibilities

include management of and technical

direction

for multidisciplinary

science

and engineering

research teams focused

on a wide range of integrated

energy and environmental

technologies.

Specific program areas of interest

include clean and efficient

use of low-grade

fuels, matching

of fuel characteristics to system design and operating

parameters,

development

of advanced

power systems based on low-grade

fuels, fundamentals

of low-grade

fuel combustion,

ash behavior

in low-grade fuel conversion

systems,

and analysis

of inorganic

materials

in low-grade

fuels. Projects emphasize

a cradle-to-grave

approach

from resource

assessment,

to optimum

utilization systems, to minimization

of emissions

and waste management

featuring

by-product

utilization. 2004-Present: Adjunct

Professor,

Physics,

UND. 1994-20t)4: Adjunct

Assistant

Professor,

Physics,

UND. 1983-2004: Associate

Director,

Industrial

Relations

and Technology

Commercialization,

EERC, UND. Dr. Jones' responsibilities

include

planning,

staffing,

and technical

direction

of combustion and gasification

research,

including

projects

in combustion

chemistry

or gasification chemistry, behavior

during

coal utilization,

fluidized-bed

combustion,

coal-water

fuels, SO•/NO• removal,

and particulate

removal

and characterization.

Special emphasis

was given to
A-2low-rank coal systems;

activities

ranged from field testing of full-scale

power plants, topilotscale studies,

to laboratory

investigations

that examine

both l-uel and system characteristics

and their impacts on overall performance. 1990-1994: Adjunct

Professor,

Department

of Chemical

Engineering,

The University

of Utah, Salt Lake City, Utah. 1979-1983: Grand Forks Energy Technology

Center,

U.S. Department

of Energy.

Dr. Jones' responsibilities included

technical

direction

of research

and development

projects

related to combustion technology

for low-rank

coals, with specific

responsibility

for fundamental

research
on pulverized

coal combustion.

Directed

research

on new, specialized

analytical

procedures

for determination of inorganics

and trace elements

in coal and materials

derived

from coal combustion and conversion

processes.

Instrumentation

included

methods

Auger/ESCA spectrometer, scanning

electron

microscope,

x-ray diffraction,

x-ray fluorescence,

argon plasma spectrometer, and atomic absorption

spectrometer. Professional Memberships Adjunct Membership,

Graduate

Faculty,

University

of North Dakota,

1994 Chair, ASME Research

Committee

on Corrosion

and Deposits

from Combustion

Gases Utility Advisory

Task Force for DOE-FE

Study on RCRA Impact on Coal-Fired

Utilities Sigma Xi The Scientific

Research

Society Society for Applied

Spectroscopy The Combustion

Institute North Dakota Academy

of Science Publications and Presentations Has authored

or coauthored

over 80 publications

A-3JOHN P. KAY Research Manager Energy & Environmental

Research

Center (EERC),

University

of North Dakota (UND) 15 North 23rd Street, Stop 9018, Grand Forks, ND 58202-9018

USA Phone (701) 777-5000,

Fax (701) 777-5181,

E-Mail: jkay@undeerc.org Principal Areas of Expertise Mr. Kay's principal

areas of interest

and expertise

include

applications

of scanning

electron microscopy (SEM), x-ray diffraction

(XRD), and x-ray fluorescence

(XRF) techniques

to the analysis of coal, fly ash, biomass,

ceramics,

high temperature

specialty

alloys, and biological tissue. He is also interested

in computer

modeling

systems,

high-temperature

testing systems, and gas separation

processes

and is a FLIR Systems,

Inc.-certified

infrared

thermographer.

He is currently involved

in field-testing

site management

and sampling

techniques

for mercury

control in combustion

systems. Qualifications B.S., Geological

Engineering,

University

of North Dakota,

1994. Associate Degree,

Engineering

Studies,

Minot State University,

1989. Professional Experience 2005-Present: Research

Manager,

EERC,

UND. Mr. Kay's responsibilities

include

the management and supervision

of research

involving

the design and operation

of bench-, pilot-, and demonstration-scale equipment

for development

of clean coal technologies.

The work also involves the testing and development

of fuel conversion

(combustion

and gasification)

and gas cleanup systems

for the removal

of sulfur, nitrogen,

particulate,

and trace elements. 1994-2005: Research

Specialist,

EERC, UND. Mr. Kay's responsibilities

included

conducting SEM, XRD and XRF analysis

and maintenance;

creating

innovative

techniques

for the analysis and interpretation

of coal, fly ash, biomass,

ceramics,

alloys, high-temperature

specialty

alloys, and biological

tissue; managing

the day-to-day

operations

of the Natural

Materials

Analytical Research Laboratory;

supervising

student workers;

developing

and performing

infrared

analysis methods in high-temperature

environments;

and performing

field work related to mercury control in combustion

systems. 1993-1994: Research

Technician,

Agvise Laboratories,

Northwood,

North Dakota.

Mr. Kay's responsibilities included

receiving

and processing

frozen soil samples

for laboratory

testing of chemical penetration;

maintaining

equipment

and inventory;

and training

others in processing techniques utilizing

proper laboratory

procedures. 1991-1993: Teaching

Assistant,

Department

of Geology

and Geological

Engineering,

UND. Mr. Kay taught Introduction

to Geology

Recitation,

Introduction

to Geology

Laboratory,

and Structural Geology.

Responsibilities

included

preparation

and grading

of assignments

and administering and grading class examinations.

A-41990-1992: Research

Assistant,

Natural

Materials

Analytical

Laboratory,

EERC,

UND. Mr. Kay's responsibilities

included

operation

of an x-ray diffractometer

and interpretation

and manipulation of XRD data; performing

software

manipulation

for analysis

of XRD data; performing maintenance

and repair of the XRD machine

and sample carbon coating machine; preparing samples

for XRD and scanning

electron

microscope

analysis;

and performing

point count analysis

on the scanning

electron

microscope. Professional Memberships ASM International American Ceramic

Society Microscopy Society of America Publications and Presentations Has authored

or coauthored

numerous

publications

A-5BRANDON M. PAVLISH Research Engineer Energy & Environmental

Research

Center (EERC),

University

of North Dakota (UND) 15 North 23rd Street, Stop 9018, Grand Forks, ND 58202-9018

USA Phone (701) 777-5000,

Fax (701) 777-5181,

E-Mail:

bpavlish@undeerc.org Principal Areas of Expertise Mr. Pavlish's

principal

areas of interest and expertise

include gas separation

technologies,

carbon dioxide sequestration,

activated

carbon technologies,

and emission

control related to mercury, sulfur, and particulates. Qualifications B.S., Chemical

Engineering,

University

of North Dakota,

2006 Professional Experience 2006-Present: Research

Engineer,

EERC,

UND,

Grand

Forks,

ND. Mr. Pavlish's responsibilities include

preparing

proposals,

interacting

with industry

and government organizations, researching

literature,

designing

and conducting

experiments

as a principal investigator, performing

calculations

and interpreting

data, writing technical

reports and papers, and presenting

information.

Current

projects

involve

mercury

control technologies,

biomass

for energy, and hydrogen

production. 2002-2006: Student

Engineer,

EERC, UND, Grand Forks, ND. Mr. Pavlish's

responsibilities included: Performed a broad range of engineering

functions

including

literature

research,

conducting experiments (lab- and bench-scale

testing),

pilot-scale

testing, sampling

and sample tracking, tracking project activities,

data reduction,

writing and presenting

technical

results, proposal writing, presenting

at conferences,

and preparation

of technical

papers and project reports. Specific EERC intern/coop

experience

in hydrogen:

Involved

in the preparation

of the Hydrogen short-course, literature

searches,

ChemCad

simulations

related to hydrogen

production,

hydrogen production via ethanol + water and catalyst reactions. During intern/coop

at the EERC was involved

in numerous

projects

that were focused

on emissions control. The primary

focus of the work completed

during this time was mercury

control technologies, and included

pilot- and bench-scale

testing, data reduction,

proposal

writing, technical reporting,

and presentation. Professional Memberships American Institute

of Chemical

Engineers PabHcations and Presentations Has coauthored

numerous

publications

A-6EERC ,

RICHARD L. SCHULZ Manager, Analytical

Research

Laboratory Energy & Environmental

Research

Center (EERC),

University

of North Dakota (UND) 15 North 23rd Street, Stop 9018, Grand Forks, ND 58202-9018

USA Phone (701) 777-5000,

Fax (701) 777-5181,

E-Mail:

rschulz@undeerc.org Principal Areas of Expertise Flue gas emissions

testing of combustion

gases produced

from coal-based

fuels, both on-site and in the field. Qualifications B.S., Chemistry,

University

of North Dakota,

1973. Professional Experience 1994-Present: Manager,

Particulate

Research

Laboratory,

EERC,

UND. Responsibilities include conducting

and overseeing

emissions

testing at bench-, pilot-, and full-scale

facilities. Field work includes

sampling

at industrial

process sites and coal-fired

power plants. Recent work includes a heavy emphasis

on mercury

continuous

emission

monitors,

measurement,

and control technologies. 1990-1994: Research

Specialist,

EERC, UND. Responsibilities

included

performing

particle sampling and sizing including

EPA-5 dust loading,

impactors,

SASS training,

multicyclone,

and laser particle-size

analysis.

Performed

EPA wet tests for flue gas analysis.

Other work included bench-scale testing of fly ash characteristics,

equipment

fabrication

and modification,

and supervision and coordination

of lab activities

for the personnel

in the particulate

lab bothinhouse and on field trips. 1985-1990: Pilot Plant Operator,

EERC,

UND. Responsibilities

included

assisting

in the operation and maintenance

of several types of test combustors

used to research

various aspects of low-rank coal combustion

and utilization.

Performed

several types of testing, including

flue gas monitoring of SO2, NO, NOx, CO, CO2, O•_, unburned

hydro-carbons,

and particulates. Performed field tests on actual flue gas emissions,

including

EPA dust loading and gas sampling. Field work involved

setting up sample systems,

calibration

of instruments

and equipment,

and collection of samples.

Additional

duties as shift supervisor

included

coordinating

the work of other operators

and preparing

various types of coal for use in the test combustors. 1981-1982: EG&G,

Washington

Analytical

Services,

Grand Forks Energy Technology

Center, Grand Forks, North Dakota.

Responsibilities

included

performing

duties in the operation

of pilot plant test facilities

used in conjunction

with low-rank

coal research.

Responsible

for testing, repair, and calibration

of equipment

used to sample particulates

in the field and at the pilot plant facilities.

A-71973-1977: Teacher,

Fisher School

District,

Fisher,

Minnesota.

Responsibilities planning and developing

a curriculum

for high school chemistry

and physics classes. Publications and Presentations Has coauthored

numerous

publications included

A-8.lAY R. GUNDERSON Research Engineer Energy & Environmental

Research

Center (EERC),

University

of North Dakota (UND) 15 North 23rd Street, Stop 9018, Grand Forks, ND 58202-9018

USA Phone (701 777-5000,

Fax (701 777-5 81, E-Mail:

jgunderson

@ undeerc.org Principal Areas of Expertise Mr. Gunderson's

principal

areas of interest and expertise

include fireside

performance

testing, mercury sampling,

design of pilot-scale

equipment,

and full-scale

performance

evaluation

for coal-, oil-, and biomass-fired

boilers. Qualifications M.S. Studies,

Chemical

Engineering,

University

of North Dakota,

1987-present. B.S., Chemical

Engineering,

University

of North Dakota,

1987. Professional Experience 1988-Present: Research

Engineer,

Fuels Performance,

EERC,

UND. Mr. Gunderson's responsibilities involve pilot-scale

combustion

projects

for residential-,

commercial-,

andutilityscale applications

of coal-fired

combustion

systems,

including

fuel characterization,

emission monitoring and testing, evaluation

of flame stability,

and evaluation

of ash fouling potential.

His duties include documentation

and reporting

of pilot-scale

testing results and relating

these results to the operation

of full-scale

units. Mr. Gunderson

has also managed

numerous

pilot-scale projects investigating

ash fouling and gaseous

emissions

for oil-fired

and biomass-fired

systems. 1988: Research

Assistant,

Combustion

and Environmental

Systems

Research

Institute,

Energy and Mineral

Research

Center, UND. Mr. Gunderson's

responsibilities

involved

the development of a coal-water

fuel-fired

residential-

and commercial-scale

furnace. Professional Memberships American Institute

of Chemical

Engineers Publications and Presentations Has coauthored

numerous

publications

A-9EERC

KIRK D. WILLIAMS Research Engineer Energy & Environmental

Research

Center (EERC),

University

of North Dakota (UND) 15 North 23rd Street, Stop 9018, Grand Forks, ND 58202-9018

USA Phone (701) 777-5000,

Fax (701 777-5181,

E-Mail:

kwilliams

@ undeerc.org Principle Areas of Expertise Mr. Williams'

principle

areas of expertise

and interest include materials

engineering,

analytical metallurgy, advanced

structural

composites,

mechanical

engineering,

and thermal

imaging applications. Mr. Williams

has additional

expertise

in applied

environmental

engineering, applied and theoretical

geophysical

techniques,

hydrogeology,

ground

and surface

water modeling techniques,

geodetic

global positioning

surveying,

and geographical

information systems. Qualifications M.S., Geological

Sciences,

University

of California,

Riverside,

1998. B.S., Geophysics/Computer Science,

University

of California,

Riverside,

1995. Professional Experience 2001-Present: Research

Engineer,

EERC, UND. Mr. Williams

is presently

involved

in several projects related to renewable

energy;

carbon capture

and sequestration;

hydrogen

end use demonstration, education,

and outreach;

and water quantity

and quality issues. Mr. Williams

is working

with commercial

partners

to lower the overall cost of current biogas treatment technoiogy

while maintaining

the efficiency

for smaller

applications.

He is also guiding the development

of more economical

and durable

stationary

power generation equipment that is capable of utilizing

low-Btu

fuel sources derived

from renewable

sources. Mr. Williams

has a working

knowledge

of carbon credit trading as it applies to CO•_ capture and sequestration and how this relates to methane

gas capture from landfill and wastewater

treatment plant sites. He is also knowledgeable

with compliance

regulations

related to CO2 capture

and sequestration issues and is experienced

with the basic procedures

and requirements

of combustion gas sampling. Mr. Williams'

involvement

with hydrogen

education

and outreach

has led to the successful production of an introductory

video that details H•_ production

and end uses in the upper Midwest along with a half dozen fact sheets spanning

H• safety, production,

and utilization.

He has general experience

with electrolyzers,

hydrogen

internal

combustion

engine conversions,

and the system integration

of H•_-fueled

PEM fuel cell stacks with electric drive units. Mr. Williams

has demonstrated

responsibility

for numerous

local and national

projects

involving surface water and groundwater

quality

modeling

and compliance

with federal

and state regulations. He is involved

with regional

NPDES

Phase II storm water ruling; phosphorus

fate and transport

issues; and in-basin

alternative

water supply options.

Mr. Williams

also has

A-10experience reviewing,

preparing

and submitting

environmental

impact statements

to the EPA in compliance with the National

Environmental

Policy Act. Mr. Williams

has demonstrated

skills in high-temperature

research

on metal alloys and ceramics, infrared imaging

and analysis

of high-temperature

combustion

processes,

and the corrosion properties of flowing

slag on ODS alloys MA956

and MA754

utilizing

the dynamic

slag application furnace.

Mr. Williams

also has extensive

thermal

imaging

knowledge

and experience conducting energy audits and providing

nondestructive

thermal

imaging

analysis

forhightemperature applications. Ongoing duties include authoring

proposals,

managing

funded projects,

interacting

with industry and government

organizations,

researching

literature,

designing

and conducting

effective experiments as a principal

investigator,

performing

calculations

and interpreting

data, writing technical reports and papers, and presenting

information. 2000-2001: Environmental

Scientist,

Camp Dresser

& McKee,

Western

Division.

Mr. Williams' responsibilities included

providing

groundwater

modeling

and characterization

for evaluation

of extraction and recharge

projects;

extensive

research

and reporting

on storm water pollution control and management,

groundwater

recharge

systems,

storm drain inlet cleaning,

litter solids removal device evaluation,

and storm water monitoring,

sampling,

and analysis

plans; meteorological analysis

for storm event coordination

and storm water management

projects;

soil vapor extraction

and gas flux measurements;

and analytical

field hydrogeology

including groundwater well installation,

monitoring,

and water sample analysis. 2000: Contract

Geophysicist,

Parsons

Engineering

Science,

Unexploded

Ordinance

Division, Fort Ord Project.

Mr. Williams

provided

field data collection

and processing

expertise

including data reduction,

post processing,

and interpretation

leading to a final dig list. 1995-2000: Staff Research

Associate,

Department

of Earth Sciences

Institute

of Geophysics

and Planetary Physics,

University

of California,

Riverside.

Mr. Williams'

responsibilities

included providing project

field management

for investigation

and remediation

of groundwater contamination studies;

collection

of geodetic

GPS and gravity

survey data; managed

field seismic refraction/reflection line data collection,

processing,

and interpretation;

performed hydrogeologic computer

simulation

design,

calibration,

validation,

and sensitivity

analysis; developed detailed

subsurface

fluid flow and mass transport

models;

performed

hydrochemical investigations; studied environmental

hydrogen

and oxygen

isotope effects on characterization and applications

to hydrologic

evaluations;

prepared

site maps using GIS application

software; served as a teaching

assistant

for introductory

geophysics,

mineralogy

and crystallography,

and evolutionary geology;

reviewed

environmental

proposals

and reports;

authored

research proposals and operational

grants. Also served as an instructor

for mathematics,

physics,

and applied geophysics. Professional Memberships American Geophysical

Union Geological Society of America American Association

of Petroleum

Geologists Association of Ground Water Scientists

and Engineers

A-IICertifications ITC

Level and II Infrared

Thermography Publications and Presentations Has attthored

or coauthored

numerous

publications

A-[2EERC

ROBERT R. JENSEN Research Manager Energy & Environmental

Research

Center (EERC),

University

of North Dakota (UND) 15 North 23rd Street, Stop 9018, Grand Forks, ND 58202-9018

USA Phone (701) 777-5000,

Fax (701) 777-5181,

E-Mail:

bjensen@undeerc.org Principal Areas of Expertise Mr. Jensen's

principal

areas of interest

and expertise

include

development

of computerized models and other computer-related

tools. Mr. Jensen has most recently

been involved

in several modeling projects

for ash deposition

and fouling models for coal-fired

power systems. Education B.S., Computer

Science

and Mathematics

(minor in Data Processing),

Bemidji

State University, Bemidji, Minnesota,

1984. Professional Experience 1996-Present: Research

Manager,

EERC,

UND. Mr. Jensen's

responsibilities supervision of projects

and personnel

dealing with computer

models and databases.

include
1994-1996: Research

Specialist,

EERC, UND. Mr. Jensen's

responsibilities

included

designing and implementing

graphical

interface

for groundwater

modeling

in Microsoft

Windows environment using Borland

C++4.0. 1987-1994: Lecturer/Graduate

Teaching

Assistant,

UND. Mr. Jensen's

responsibilities

included "C" programming

language

on several

platforms,

computer

programming

I (Modula-2

and Pascal), computer

programming

I lab, programming

in BASIC

(Microsoft

QBASIC), introduction to computers,

introduction

to computers

lab (Microsoft

Works). 1989-1990: Graduate

Research

Assistance,

UND. Mr. Jensen's

responsibilities

included developing expert system

for airline gate scheduling

for an Airport

Airline

Operation Management project. 1989-1990: Lecturer,

University

of North Dakota Lake Region,

Grand Forks Air Force Base. Mr. Jensen's

responsibilities

included

instructing

"C" programming

language

(Borland

Turbo C). 1985-1987: System

Manager,

Strom Engineering,

Contracted

to 3M Company.

Mr. Jensen's responsibilities included

system administrator

on UNIX PDP 11/34 and RT-It PDP 11/34. Developed software

for the interface

to the 3M laser imager, decode,

transfer,

and print medical images from magnetic

tape, develop

utility programs

for Electrical

Engineering

group.

A-131984-1985: Software

Engineer,

Northern

Micro Systems.

Mr. Jensen's

responsibilities

included programming in Z-80 assembly

language

to develop

an editor for the KROY

80k lettering machine. This project has given me a working

knowledge

of LCD display controls,

counter

time chips, stepper motor controls,

and a simple functioning

operating

system. Professional Memberships Upsilon Pi Epsilon

honor society for the computing

sciences Publications and Presentations Has authored

and coauthored

numerous

publications

A-14BRUCE A. DOCKTER Research Engineer Energy & Environmental

Research

Center (EERC),

University

of North Dakota (UND) 15 North 23rd Street, Stop 9018, Grand Forks, ND 58202-9018

USA Phone (701 777-5000,

Fax (701 777-518

I, E-Mail:

bdockter@

undeerc.org Principal Areas of Expertise Mr. Dockter's

principal

areas of interest and expertise

include physical

and chemical

analysis

of fly ash and examination

of coal ash for utilization

in high- and low-volume

applications.

In addition, he has also worked extensively

in the field of high-temperature

research

on the physical and chemical

properties

of coal ashes and slags. Qualifications Registered Professional

Engineer,

1993. M.E., Civil Engineering,

University

of North Dakota,

1991. B.S., Civil Engineering,

University

of North Dakota,

1983. Professional Experience 1991-Present: Research

Engineer/Manager,

Fuels and Materials

Research

Laboratory,

EERC, UND. Mr. Dockter's

responsibilities

include supervisory

management

of laboratory

projects

and testing procedures

and coordination

of research

efforts between

laboratory

facilities

and EERC project managers

for evaluating

coal by-products

for utilization

options.

Tasks also include methodology evaluations,

proposal

writing,

and paper publications

and presentations. 1985-1991: Chemist

II/Manager,

Coal By-Products

Utilization

Laboratory,

EERC, UND. Mr. Dockter's responsibilities

included

daily operation

of laboratory

emphasizing

setting daily work objectives, supervision

of full-time

and student employees,

and general lab maintenance.

He was also responsible

for training

new employees,

conducting

seminars,

keeping

test result books, and writing final report papers. 1984-1985: Chemist

I, Fine Coal Cleaning

Project,

Grand Forks Energy Research

Center. Mr. Dockter's responsibilities

included

data interpretation

for methods

including

oil agglomeration and froth flotation. 1983-1984: Engineering

Technician

III, Fine Coal Cleaning

Project,

Grand Forks Energy Research Center.

Mr. Dockter's

responsibilities

included

performing

washability

and other beneficiation tests for the physical

separation

of mineral-rich

materials

from coal samples. Professional Memberships American Society for Testing and Materials National Society of Professional

Engineers Transportation Research

Board Publications and Presentations Has authored

or coauthored

over 70 publications

A-15EERC

DONALD L. TOMAN Research Scientist Energy & Environmental

Research

Center (EERC),

University

of North Dakota (UND) 15 North 23rd Street, Stop 9018, Grand Forks, ND 58202-9018

USA Phone (701 777-5000,

Fax (701 ) 777-5181,

E-Mail:

dtoman @ undeerc.org Principal Areas of Expertise Mr. Toman's

principal

areas of interest and expertise

include design, fabrication,

and operation of bench-,

intermediate-,

and pilot-scale

combustion

systems

and full-scale

testing of gaseous and particulate

emissions. Qualifications B.S., Natural Sciences,

University

of North Dakota,

1980. Professional Experience 1989-Present: Research

Scientist,

Systems

Development,

EERC,

UND. Mr. Toman's responsibilities include

designing,

fabricating,

and operating

various

types of bench-scale systems to produce

and collect chars and ash from coal under closely controlled

conditions;

fullscale utility boiler testing and collection

of gaseous

and particulate

emissions;

collecting, interpreting and reporting

of data; and preparing

budgets,

proposals,

and reports. 1985-1989: Pilot Plant Operator

Supervisor,

Operations

Division,

EERC, UND. Mr. Toman's responsibilities included

supervision

and evaluation

of operations

personnel;

planning

project and work schedules;

maintaining

production

records;

quality assurance

and quality control;

and ensuring that regulations

and rules were observed

on housekeeping,

conduct,

and safety. 1983-1985: Pilot Plant Operator

III, Pilot Plant Operations,

Coal Utilization

Research

Division, Energy Research

Center, UND. Mr. Toman's

responsibilities

included

supervision

of personnel and facility operations,

maintenance,

and trouble-shooting

of pilot plant test equipment. 1982: Operations

Group Supervisor,

EG&G Washington

Analytical

Services

Center, Inc., Grand Forks, North Dakota.

Mr. Toman's

responsibilities

included

all aspects of combustion

pilot plant operations, including

supervision

and evaluation

of operations

personnel,

scheduling,

and supervising performance

of combustion

pilot plant testing,

reviewing

data collected

from combustion pilot plant testing,

preparing

weekly

summaries

and monthly

reports,

and documenting work performed

by the Operations

Group. 1982: Shift Supervisor,

Operations

Group, EG&G Washington

Analytical

Services

Center,

Inc., Grand Forks, North Dakota.

Mr. Toman was responsible

for all aspects of facility operation

and supervision of operations

personnel

during shift. 1980-1982: Pilot Plant Operator,

Operations

Groups,

EG&G Washington

Analytical

Services Center, Inc., Grand Forks, North Dakota.

Mr. Toman's

responsibilities

included

operations,
A-16maintenance, data collection,

and trouble-shooting

of pilot plant equipment.

Pilot plant equipment included

two pulverized

coal-fired

combustors,

an AFBC coal-fired

combustor,

a wet scrubber flue gas desulfurization

test unit, a direct injection

flue gas desulfurization

test unit, and various coal processing

equipment

(pulverizer,

crusher,

classifier,

dryer, conveyors,

and lift trucks). Experienced

in the operation

of solid feeders,

particulate

collection

equipment,

flue gas sampling equipment,

and process instrumentation. 1980: Lab Technician,

Grand Forks Energy Technology

Center,

UND, Grand Forks, North Dakota. Mr. Toman's

responsibilities

included

preparing

samples

for analysis

and performing routine coal and ash analysis. Publications and Presentations Has authored

or coauthored

numerous

publications

A-t7EERC

WILLIAM I. "JIB" WILSON

IV Research Specialist Energy & Environmental

Research

Center (EERC) University of North Dakota (UND) 15 North 23rd Street, Stop 9018 Grand Forks, ND 58202-9018

USA Phone (701) 777-5000,

Fax (701) 777-5181 E-Mail: j wilson @ undeerc.org Principal Areas of Expertise Mr. Wilson's

principal

areas of interest

and expertise

include

residential

energy efficiency, residential construction,

and real estate sales and finance. Qualifications A.S., Electronic

Engineering

Technologies,

Maui Community

College,

Kahului,

Hawaii,

1998. Real Estate Securities

and Syndication

Institute,

Carmel,

California,

1979. Professional Experience 2006-Present: Research

Specialist,

EERC, UND. Mr. Wilson's

work focuses

on residential building programs,

environmental

systems,

and energy conversion

technologies.

Hisresponsibilities include proposal

preparation,

writing reports and papers, and presentation

of research findings. 2005-2006: Technician,

HB Sound & Light, Grand Forks, North Dakota.

Mr. Wilson's responsibilities included

assisting

in commercial

installations

of projectors

and sound systems, computer networks,

and surveillance

cameras;

repairing,

maintaining,

and troubleshooting

GF Public Schools

sound systems

for the hearing

impaired;

and assisting

in the setup of concert sound systems,

including

the setup and operation

of concert lighting. 1998-2004: Residential

Program

Manager,

Maui Electric

Company,

Ltd (MECO),

Kahului, Hawaii. Mr. Wilson's

responsibilities

included

expanding

the number

of Residential

Efficient Water Heating

(REWH)

technologies

installed

in homes throughout

Maui County,

meeting shareholders incentives,

kW and kWh goals, and financial

goals; retaining

customers

through

the Demand Side Management

Program;

providing/assisting

in monthly,

semiannual,

and annual reports that are filed with the PuNic Utilities

Commission;

and developing

and maintaining cooperative relationships

between

community,

industry,

and state and local government

to educate the punic on energy

efficiency

to decrease

Maui's

dependence

on fossil t\•els. Achievements include the following:

® Increased

the number of solar water-heating

(SWH) systems

installed

on new homes from 16% to over 40% in 6 years, averaging

a 22.5% increase

per year.

• Developed

and coordinated

multidisciplinar,v

contracts

between

home owners,

builders, developers, lenders,

Fannie Mae, U.S. Environmental

Protection

Agency

(EPA), and other

A-18key county,

state, federal,

and private agency supervisors

and staff personnel.

Provided and or assisted

in creating

monthly,

semiannual,

and annual reports that are filed with the Public Utilities

Commission

and writing county and federal grants.

• Improved

the way homes were being built by recruiting

Hawaii's

first builders

and developers to make solar water heating a standard

feature in all their new homes.

• Created

and presented

education

seminars

for Hawaii's

Building

Industry

Association, Hawaii Association

of Realtors,

state and local lenders,

and the Maui Contractor's Association's Annual Home Show.

• Assisted

in creating

Maui Electric's

Commercial

Solar Program.

• Contributed

to the creation

of the Solar Water Heating

Test Center for Maui Community Colleges Sustainable

Technology

Program.

• Received

the Outstanding

Achievement

Award

U.S. Department

of Energy,

Energy Star Homes Program

-2002, 2003, and 2004.

• Recognized

by the state of Hawaii's

Department

of Business,

Economic

Development,

and Tourism for accomplishments

with Maui's Building

Industry.

• Best Progress

Award

One of three National

Awards,

awarded

by the U.S. Department

of Energy.

• Researched

and cowrote

county and federal grants.

• Published

in industry

and local magazines. 1996-1998: Intern for Department

of Defense

Contract,

Maui High Performance

Computer Center, Kihei, Hawaii.

Mr. Wilson's

responsibilities

included

assisting

in the design and construction of an eight-node

NT Cluster at the Maul High Performance

Computer

Center for the U.S. Department

of Defense

and assisting

in writing Perl scripts. 1996-1998: Solar Inspector,

Maui Electric

Company,

Ltd, Kahului,

Hawaii.

Mr. Wilson's responsibilities included

verifying

compliance

of over 85 items in Maui Electric's

solar water heating program's

standards

and specifications

by inspecting

installations

done by participating contractors; serving as primary

troubleshooter

for customers

complaining

about the lack of hot water; and assisting

in troubleshooting

the cause of high bill complaints. 1992-1997: Owner,

Light and Sound Tech, Kihei, Hawaii.

Mr. Wilson's

responsibilities included working

as a light and sound engineer

for shows and productions

for the entertainment community in the state of Hawaii,

creating

and maintaining

multiple

light and sound contracts for numerous

national

and statewide

performing

arts, entertainment,

and lighting

and sound companies. 1983: Principal

Broker,

ERA Pacific Land, Wailuku,

Hawaii.

Mr. Wilson's

responsibilities included negotiating

and processing

sales contracts,

leases, agreements,

deeds, title searches,

etc. while managing

day-to-day

operations. 1983-1990: Real Estate Licensing

Instructor,

ERA Pacific Land dba Maui School of Real Estate, Wailuku, Hawaii.

Mr. Wilson's

responsibilities

included

instructing

students

on real estate mathematics for real estate licensing

course on the island of Maui. Taught weekly classes as well
as participated

in class recruitment

and real estate course tutoring.
A-19Publications and Presentations Has authored

and coauthored

numerous

publications

and symposium

presentations

on residential energy efficiency,

construction,

and finance.

A-20EERC

KYLE E. MARTIN Research Engineer Energy & Environmental

Research

Center (EERC),

University

of North Dakota (UND) 15 North 23rd Street, Stop 9018, Grand Forks, ND 58202-9018

USA Phone (701) 777-5000,

Fax (701) 777-5181,

E-Mail:

kmartin @ undeerc.org Principal Areas of Expertise Mr. Martin's

principal

areas of interest and expertise

include cogeneration,

biomass

energy, and fuel cells. His experience

also includes

power plant testing for pollutants

such as ammonia, chlorine, sulfur compounds,

and mercury

as well as development

and testing of continuous emission monitors;

thermomechanical

pulping;

and agricultural

processing

system

design, development, and installation,

including

a growth scoring system and a light canopy project. Qualifications M.S., Chemical

Engineering,

University

of North Dakota,

2006 B.S., Chemical

Engineering,

University

of North Dakota,

2002 B.S., Chemistry,

University

of North Dakota,

2001. Professional Experience 2001-Present: Research

Engineer,

EERC, UND. Mr. Martin's

current responsibilities

include research focused

on cogeneration,

biomass

energy,

and fuel cells. Duties include

proposal preparation, system design and construction,

experimental

planning

and design, preparation

of reports, and presentation

of results. Mr. Martin's

experience

at the EERC also includes

power plant testing for pollutants

such as ammonia,

chlorine,

sulfur compounds,

and mercury

as well as development and testing of continuous

emission

monitors. 2000-2001: Process

Engineer,

Champion/International Paper, Sartell, Minnesota.

Mr. Martin's responsibilities focused

on thermomechanical

pulping,

including

optimizing

the system and daily troubleshooting. Projects

involved

development

of a quality control reporting

system,

justification of projects,

and experiments

to improve

profit. 1999: Project Engineer,

Cargill Oilseeds

Ltd., Clavette,

Saskatchewan,

Canada.

Mr. Martin's responsibilities included

designing,

pricing,

ordering,

and overseeing

installation

of a new $500,000 system which involved

managing

up to 30 employees. 1998: Research

Engineer,

Agriculture

& Agri-Food,

Scott, Saskatchewan,

Canada.

Mr. Martin's responsibilities included

recording

experimental

data, mixing

and applying

chemicals,

and performing special projects,

including

the development

of a new growth scoring system and a light canopy project. Publications and Presentations Has coauthored

numerous

publications

A-2IERICK J. ZACHER Research Assistant Energy & Environmental

Research

Center (EERC),

University

of North Dakota (UND) 15 North 23rd Street, Stop 9018, Grand Forks, ND 58202-9018

USA Phone (701) 777-5000,

Fax (701) 777-5181,

E-Mail:

ezacher@undeerc.org Principal Areas of Expertise Mr. Zacher's

principal

areas of interest and expertise

include ash chemistry,

leaching

procedures, ultratrace mercury

analysis

with a double-gold

amalgamation

atomic fluorescence

apparatus, environmental impacts

of coal combustion

by-product

(CCB) use and disposal,

environmental sampling analysis,

and surface and groundwater

environmental

impacts.

Recent research

has included an extensive

mercury

and air toxic elements

project and work in various other projects involved in evaluating

the environmental

impacts

of CCB utilization.

Mr. Zacher has laboratory experience with organomercury

compound

analysis

utilizing

gas chromatography

organic synthesis, atomic fluorescence

spectroscopy,

atomic absorption

and inductively

coupled

argon plasma spectroscopy,

ultraviolet

and fluorescence

analysis,

gas chromatography,

and ion chromatography. Qualifications B.S. Environmental

Geology

and Technology,

University

of North Dakota,

May 2005. Professional Experience 2005-Present:Research

Scientist,

EERC,

UND. Mr. Zacher's

responsibilities

include performing laboratory

experiments

to evaluate

the characteristics

of industrial

by-products, especially coal combustion

by-products,

including

sample preparation;

environmental

performance testing (leaching,

elevated-

and ambient-temperature vapor-phase

release experiments

for trace elements

and microbiologically

mediated

release experiments);

and instrumental

analyses, including spectrophotometric methods

(atomic

fluorescence,

atomic

emission,

and atomic absorption) and gas chromatography

with solid-phase

microextraction. 2002-2005: Research

Assistant,

Coal Ash Research

Laboratory,

EERC, UND. Mr. Zacher's responsibilities included

research

focused

primarily

on the environmental

impacts

of CCB use and disposal,

ultratrace

mercury

analysis,

and data interpretation

and management. Summer 2001: Laboratory

Assistant,

North Dakota

Department

of Health

Chemistry Laboratory. Mr. Zacher's

responsibilities

included

environmental

sample preparation

for organic contaminant analysis,

gas chromatographic

organic contaminant

analysis

for drinking

water and groundwater samples,

biological

oxygen demand

(BOD) analysis

of environmental

samples,

total dissolved solids (TDS) analysis

of surface

water samples,

performance

of the toxicity characteristic leaching

procedure

(TCLP)

on various

environmental

samples,

and data interpretation.

A-22Professional Membership Phi Beta Kappa Publications and Presentations Has coauthored

several publicationsSTEPHEN E. SOLLOM Research Engineer Energy & Environmental

Research

Center (EERC),

University

of North Dakota (UND) 15 North 23rd Street, Stop 9018, Grand Forks, ND 58202-9018

USA Phone (701) 777-5000,

Fax (701) 777-5181,

E-Mail:

ssollom@undeerc.org Principal Areas of Expertise Mr. Sollom's

principal

areas of interest and expertise

include pilot-scale

combustion

systems

and emission control related to mercury,

sulfur, and particulate

matter. Qualifications B.S., Chemical

Engineering,

University

of North Dakota,

2006. Professional Experience 2006-Present: Research

Engineer,

EERC,

UND. Mr. Sollom's

responsibilities

include researching literature,

designing

and conducting

effective

experiments,

performing

calculations and interpreting

data, and writing technical

reports and papers. Work focuses

on the pilot-scale combustion systems

and emission

control related to mercury,

sulfur, and particulate

matter. 2003-2006: Research

Assistant,

EERC,

UND. Mr. Sollom's

responsibilities

included researching the literature,

designing

and conducting

effective

experiments,

performing calculations, interpreting

data, helping

to write technical

reports and prepare

presentations. Specifically, he performed

literature

reviews

on mercury

emissions,

mercury

control technologies, and full-scale

mercury

removal;

NOx emission

and control;

SO2 emission

and control; and patents on mercury

control technologies;

drafted reports and reviewed

final data for the Leland Olds and Antelope

Valley Stations

and assisted

in pilot-scale

tests with carbon injection by calibrating

and monitoring

the feeder during pilot-scale

testing; was responsible

for data reduction

and analysis

on various aspects of the Leland Olds and Antelope

Valley Station projects; and assisted

in field trip installation

of a selective

catalytic

reduction

system at the Coyote Station. Publications and Presentations Has coauthored

numerous

publications.

A-24EERC

RAYMOND A. DEWALL Research Scientist Energy & Environmental

Research

Center (EERC),

University

of North Dakota (UND) 15 North 23rd Street, Stop 9018, Grand Forks, ND 58202-9018

USA Phone (701) 777-5000,

Fax (701) 777-5181,

E-Mail:

rdwall@

undeerc.org Principal Areas of Expertise Physical and chemical

coal cleaning

and preparation

of coal-water

fuels. Qualifications B.S., Chemistry

and Microbiology,

South Dakota State University,

1982. Professional Experience 1988-Present: Chemist

III, Applied

Chemistry,

EERC, UND. Responsibilities

includepreparation of coal-water

fuels from low-rank

and beneficiated

low-rank

coal. Utilize physical

and chemical cleaning

methods

on coal. Develop

new processes

for cleaning

coal. Analyze

and report data for reports

and publications.

Present

research

results at conferences.

Supervise students working

on the project. 1986-1988: Chemist

II, Energy and Mineral

Research

Center, UND. Responsibilities

included same tasks as above. 1985-1986: Chemist

I, Energy Research

Center, UND. Responsibilities

included

using physical coal cleaning

methods

on a database

of samples.

Analyzed

products

for moisture,

ash, sulfur, and heating value. 1983-1985: Chemist

I, Energy Research

Center, UND. Responsibilities

included

analyzing

coal liquefaction products

by wet and instrumental

analytical

methods.

Gained considerable

knowledge in the operation,

maintenance,

and repair of a gas chromatograph

andcarbon-hydrogennitrogen analyzer. 1982-1983: Lab Technician

III, Engineering

Experiment

Station,

UND. Responsibilities included setup and analysis

of products

from hot-water

drying of coal using ASTM methods

of analysis. Ordered

lab supplies

and trained students

in lab operation. Professional Memberships American Chemical

Society Publications and Presentations Has coauthored

numerous

publicatJ.ons

A-25EERC

DAVID G. WESTERMAN Research Specialist

II Energy & Environmental

Research

Center (EERC),

University

of North Dakota (UND) 15 North 23rd Street, Stop 9018, Grand Forks, ND 58202-9018

USA Phone (701) 777-5000,

Fax (701) 777-5181,

E-Mail:

dwesterman

@undeerc.org Principal Areas of Expertise Mr. Westerman's

primary

expertise

is related to the technical

aspects of soil and groundwater field work, including

the installation,

development,

and maintenance

of groundwater

monitoring wells, lysimeters,

piezometers,

tensiometers,

and other instrumentation

for the collection

of data pertaining to soils and hydrogeology;

odor control and testing equipment;

freeze-thaw

facility installation and operation;

wind monitoring

system installation,

monitoring,

and maintenance. QUALIFICATIONS Boiler School, Area Vocational

Technical

Institute

(AVTI),

East Grand Forks, Minnesota Boiler School, Wahpeton,

North Dakota Aircraft Maintenance

Jet Engine School, Sheppard

AFB, Texas, 1970 Beaver County Community

College,

Freedom,

Pennsylvania,

1970 Minnesota Class Engineer,

License

No. 1821 Professional Experience 1985-Present: Research

Specialist

II, EERC, UND. Mr. Westerman's

responsibilities

include the installation,

development,

and maintenance

of groundwater

monitoring

wells, lysimeters, piezometers, tensiometers,

and other instrumentation

for the collection

of data pertaining

to soils and hydrogeology;

installation

of barIey straw on wastewater

ponds and biofilters

for odor control; construction

and operation

of freeze-thaw

unit; construction

of wind monitoring

towers for feasibility

studies.

Other duties include

collecting

water and soil samples

for a variety of chemical analyses

and performing

various

testing

procedures

for the determination

of hydrogeologic properties

of the subsurface.

He has experience

with a variety of sampling techniques for both organic and inorganic

contaminants

in groundwater,

use of sniffometer

odor testing, and a variety of hydrogeologic

testing techniques,

including

slug tests, drawdown

and recovery tests, and pump tests. He is also experienced

in sampling

for mercury

in soils. He is adept at using neutron

soil moisture

probes,

computer

data loggers,

instrumentation

for the determination of chemical

parameters

such as pH and conductivity,

and a variety ofwatersampling devices.

He also has laboratory

experience

preparing

soil for chemical

analysis, performing dry-sieve

testing

for grain-size

analysis,

operating

filtering

equipment,

and determining soil moisture

parameters

through

the use of ASTM testing procedures.

He also worked with the EERC team on underground

coal gasification

in Thailand. 1985-1990: Maintenance

Worker

II, EERC, UND. Mr. Westerman

performed

maintenance

of EERC buildings

and equipment. 1979-1985: Boiler Operator,

LIND Boiler Plant.
A-261977-1979: Salesman,

American

National

Insurance

Company,

Grand Forks, North Dakota. 1970-1977: Military,

United

States Air Force. Mr. Westerman

performed

aircraft maintenance. Professional Memberships National Ground Water Association jet

A-27APPENDIX B EXAMPLE CALCULATIONSEXAMPLE CALCULATIONS Sample calculations

are included

for each of the calculated

parameters. OH Method

Sampling Volume of Gas Sample Vm(std)

volume of gas sample measured

by the dry gas meter, corrected to standard

conditions,

dscf Vm(std) (dscf) K• xVmcxPm Tm + 460 17.64x 45.472x

x 29.665 Vm(std)

42.190 dscf 104 + 460 Where: K

Pm 17.64 R/in. Hg Vm x Cm volume of gas sample as measured

by dry gas meter corrected for meter calibration (Cm meter calibration

coefficient)

(dcf) meter pressure

(in. Hg) meter temperature

(°F) Volume of Water Vapor Vw(std) Vw(std) (scf) Vw(std) volume of water vapor in the gas sample, corrected

to standard conditions, scf K2 x H•_O(g) 0.04715 x 137.5 6.483 scf Where: H20(g) 0.04715

ft3/g
mass of liquid collected

in impingers

and silica gel (g) Water Vapor in the Gas Stream BWS water vapor in the gas stream, proportion

by volume
BWS Vw(std) Vm(std) + Vw(std)

B-!6.483 Bws =0.1332 Dry Molecular

Weight Md Md (lb/lb-mol) Md Where: %(CO2, 02, N2, CO) Molecular Weight Ms Ms (lb/lb-mol) Ms 42.190 + 6.483 dry molecular

weight of stack gas, lb/lb-mol 0.440 x (%CO2)

+ 0.320 x (%0-2_) + 0.280 x (%N2 + %CO) 0.440 x 15.9 + 0.320 x 3.1 + 0.280 x 81.0 30.7 lb/lb-mol
percent (CO2, 02, N2, CO) by volume,

dry basis

molecular weight of stack gas, wet basis, lb/ib-mol Md x (1 -Bws) + 18.0 x Bws 30.7 x (l -0.1332)

+ 18.0 x 0.1332

29.0 lb/lb-mol Average Stack Gas Velocity Vs

Average

stack gas velocity,

ft/sec

• [-Ts +4601':2 Vs (ft/sec) K3 xCpx(Ap)"2

tavg)x•

•s•Ms _] 685+460 Vs 85.49x0.84x0.4472x 30--•-9--•..0_]

36.6ft/sec
Where:
K 3 CpAp(•p)": (•vg)
Ts Ps lb xin. Hg ]•/•- 85.49 x | lb mol pitot tube coefficient,

dimensionless velocity head of stack gas (in. Hg)
average of the square root of Ap values Stack gas temperature

(•'F) Stack pressure

(in. Hg)
B-2Isokinetic Sampling

Rate
I(%)

Where:

An percent of isokinetic

sampling,

% K• x(Ts + 460)x Vm(std)

x 144 Psx Vsx An x0x(l

Bws) 0.09450x (685 + 460)x 42.190x

144 30.49 × 36.6 x 0.0707 x 90x (l 0.1332)

0.09450% (in. Hg )(rain R x sec cross-sectional area of nozzle (in. 2) total sampling

time (min) 107%

Volume of Gas Sample

Corrected

to 7% O2 Vm*(std) volume of gas sample measured

by the dry gas meter (Vm[std]), * corrected

to 7% oxygen,

Nm 3 Vm*(std) K 5 x Vm(std)x

21 %0 2 14 Vm*(std) 0.02832

x 42.190 x 21 -3.1 14 1.188Nm
Where: K5Mercury Hg (,ug/Nm 3)

0.02832

m•/ft 3
btg Vm * (std) Hg Particulate Hg Oxidized Hg 6.99 1.188 5.88 ,ttg/Nm 3

sum of Hg from filter and nozzle rinse
sum of Hg from KCI impingers
B-3Elemental

Hg

sum of Hg fi'om H202 and KMnO4

impingers MERCURY MONITORS Corrected Mercury

Concentration

at Stack Hg STK Hg concentration,

7% O-,, dry basis, stack location,

,ug/dNm 3 Hg ST• (,ug/dNm

3) Hg STK 21-7 Hg MM X 21-%O

%H•O) × 1+• 100
2.68x 21-4.6)

x +I-•

l'85'ug/dNm3

PAC INJECTION IpAC amount of PAC injected

into duct, based on gas flow, lb/Macf [pAc (lb/Macf) FpAc X 1000X528 60 F s x(T +460) 47.8 1000x528 IpAc X 0.46 lb/Macf 60 1213.5x(300+460) Where: FpAc Fs PAC feed rate (lb/hr) stack gas flow (kscfm)
PERCENT DIFFERENCE Applied when comparing

two experimental

quantities,

E and E2, neither of which can be considered the "correct"

value. The percent difference

is the absolute

value of the difference

over the mean times 100.

B-4THIS PAGE

INTENTIONALLY LEFT

BLANK.APPENDIX C SLIPSTREAM BAGHOUSE MM

DATA

AND

TEST DESCRIPTIONC-tC-2C-5•' 0 0 0 © 0 0 0THIS PAGE

INTENTIONALLY LEFT

BLANKAPPENDIX D QUALITY ASSURANCE/QUALITY CONTROLQUALITY ASSURANCE/QUALITY CONTROL Detailed quality assurance/quality

control (QA/QC)

procedures

that were used for the flue gas-sampling activities

and implementation

of the Hg control technologies

at the Durkee Cement Facility are described

herein. The QA/QC

plan, which provided

guidelines

as to how testing activities detailed

in the site-specific

test plan were to be performed,

was adhered

to during all testing, sample preparation,

sample analysis,

and data reduction

activities. Careful consideration

was used during

on-site

flue gas monitoring

and sampling procedures to ensure that all QA/QC

requirements

were met. Sorbent

enhancement

additive (SEA) addition

and powdered

activated

carbon

(PAC) injection

systems

were installed, calibrated, and operated

with QA/QC

procedures

in mind. All analytical

work, performed

either on-site or at EERC facilities,

was performed

according

tO QA/QC

guidelines.

FLUE GAS MERCURY

MEASUREMENTS Mercury Monitoring The Tekran

Model 3300 atomic

fluorescence-based

Hg vapor analyzer

was used to continuously monitor

Hg ° and Hgtota• concentrations.

The Tekran instrument

traps the Hg vapor from the conditioned

sample

onto a cartridge

containing

an ultrapure

gold sorbent.

The amalgamated Hg is then thermally

desorbed

and detected

using atomic

fluorescence spectrometry. A dual-cartridge

design enables

alternate

sampling

and desorption,

resulting

in a nearly continuous

measurement

of the sample stream. An automatic

Hg ° permeation

source was used to calibrate

the instrument

daily. Manual

Hg ° injection

calibration

on both cartridges

was also performed

for verification.

The Tekran instrument

measures

either Hgtota! or Hg °, with an analysis occurring

approximately

every 2.5 minutes. A four-point

calibration

curve was then completed

using matrix-matched

standards.

The detector response

for a given standard

was logged and compared

to specifications

to ensure the instrument was properly

set up. A QC standard

of a known analyte concentration

was analyzed immediately after the instrument

was standardized

in order to verify the calibration.

This QC standard was prepared

from a different

stock than the calibration

standards.

The values obtained read within 5% of the true value. After the initial QC standardization

was completed,

standards
were run every ten samples

to check the slope of the calibration

curve. One in every ten samples
was run in triplicate

and spiked to verify analyte recovery.

A QC chart was also maintained

by the Energy

& Environmental

Research

Center

(EERC)

chemist

to monitor

the long-term precision of the instrument. ASTM International

Method

D6784-01 The ASTM International

Method

D6784-01

(Ontario

Hydro [OH] Method)

was used to monitor flue gas Hg concentrations

and verify MM measurements.

Hg species samples

were collected at the air heater (AH) outlet and the stack at each condition,

as outlined

in the test plan. U.S. Environmental

Protection

Agency

(EPA) methods

to determine

flue gas flow rate at both
D-1locations

were used, and EPA Reference

Methods

1-5 and 17 requirements

for isokinetic sampling were followed.

The impinger

trains were weighed

before and after sampling

to determine flue gas moisture.

The sampling

trains used in-stack

filtration

(EPA Method

17 configuration) at all sampling

locations.

All analyses

of the liquid samples

collected

using the OH Hg speciation

method

were performed

by the EERC, either on-site or at a nearby location, including the field blanks and spikes. Presampling Preparation.

All data sheets, volumetric

flasks, and petri dishes used for sample recovery

were marked

with preprinted

labels to ensure proper cross-referencing.

The liquid samples

were recovered

into premarked

volumetric

flasks, logged, and then analyzed

onsite or at a nearby location.

Filter samples

were placed in premarked

petri dishes and then taken back to the EERC,

where they were analyzed.

The prestack

filter samples

were placed in premarked containers,

logged, and then analyzed

on-site. The labels contained

identifying

data including date, time, run number,

sample port location,

and the name of the sampler. Glassware and Plasticware

Cleaning

and Storage.

All glass volumetric

flasks and transfer pipets used in the preparation

of analytical

reagents

and calibration

standards

were Class "A" as designated

by federal specifications.

Prior to being used for sampling,

all glassware

was washed with hot soapy water, rinsed with deionized

(DI) water three times, soaked in 10% V/v nitric acid for a minimum

of 4 hours, rinsed an additional

three times with DI water, and dried. The glassware

was stored in closed containers

until used at the plant. Analytical Reagents.

All acids used for the analysis

of Hg were trace metal grade. Other chemicals that were used in the preparation

of analytical

reagents

were analytical

reagent grade. The calibration

standards

used for instrument

calibration

and the QC standards

used for calibration verification

were purchased

commercially

and certified

to be accurate

within _+0.5% and traceable

to National

Institute

of Standards

and Technology

(NIST) standard

reference materials. Blanks and Spikes. As part of QA/QC,

a field blank was associated

with sampling

at each location for each test condition.

A field blank is a complete

impinger

train including

all glassware and solutions

that is taken to the field during sampling

and exposed

to ambient conditions. These sample trains were taken apart and the solutions

recovered

and analyzed

in the
same manner

as those sample trains used for sampling

activities.

The blanks were used to verify low background

levels. As part of QA/QC,

a field spike was associated

with each OH test day. A field spike was prepared by the field manager

at a level similar to the field samples.

These sample trains were then taken apart, and the solution

recovered

and analyzed

in the same manner

as those sample trains used for sampling

activities.

The target range for recovery

of a field spike is 20%. Comparison of MM and ASTM International

Method

D6784-01 Analysis Results The ASTM International

Method

D6784-01,

(OH method)

is considered

to be a reference method by EPA

for evaluating

the relative

accuracy

of MM results.

D-2THIS PAGE

INTENTIONALLY LEFT

BLANKAPPENDIX E MAIN STACK

MM

DATAThe following

graphs display the mercury

monitor

data collected

at the stack during the test program

listed by date. All data have been corrected

and are presented

on a ,ttg/Nm

basis. For days where the concentration

measured

was above 1000 ,ttg/Nm •, two graphs are provided:

a graph at full scale of concentration

to show the overall range and a graph at a maximum concentration of 1000 gg/Nm • to show more detail between

Hgto• and Hg °. The low-scale

graph
was made standard

across all days so that comparisons

between

days are more easily made. Data
are not shown during the period between

April 20 and 22 because

of a plant shutdown.

E-I00

00

0

00

0 0 0

0 0 0 0 0 0 0 0 0 uO 0 C•I•LUN/6d 'uop, eJ].uaouoo 0

0

0

0 0 0 0 0 0 0 0 0 0 0 0 O0 £0 "•" O4 •LUNl6d 'uo!leJ:l.USOUOO

E-2•WN/6d 'uo!le.•],uaouoo00

0

0 CD 0 0 0 0 0 0 0 0 (D 0 •LUN/6fl 'u0!leJ:lue0uo9O

O O

O

OO

OO 0 0

0

0

00

00

0 0 0 0 0 0 0 0 0 0 0 0 CO QO •" • •mN/6fl 'u0!•.e,q.ue0u00OO

E-4£LUN/6fl 'uo!],eJ•,ua0u09

C•

OO

O O

ooo• •o
•=

00

00

00

0 0 0 0 0 CO 0 0 0 0 0 0 0 0 O

O

00

0

00

00

sLUN/6d 'u0!•.•.u•0u0o

E-5c) c)

o

0

0 0 0 0 0 0 0 0 0 0 0 0 0 0 £LUN/6d U O!],eJ•.UeOLlO•) o o

oo

oo

o

c) o

oo

oo cLUNI6fl u0!•.e.q.ue0u0300

00 00

0

00

00

00

00

0

00

E-70

0 0 0

00

00

• LU NIGd 'UO!:],eJ],UaOUOO

0 0

00

o°

00

00

00

000

0 0 0 0 0 0 0 0 0 0 0 CO r•O •

00

0

0

0

00

0

sLUNlfid uo!].eJ].uaouoc)oc)

o

oo

oo

oo

oo

o

E-IOO0

0

0

00

0 O

0 O

00

0

00

E-I10

0

00

00

00

00

00

00

0oo

o

o o

E-13o o

o

o o

o o

o

o

E-14OO 00

00

0 0

00

00

00 sLUN/6d 'uo!].e.q.uaouo::)

E-t5oo

oo

oo

o

o

o ooo

CD

00 £tUN/6d 'uo!•.eJ•.Ua0UOO ILl O

•D O

O O

O

•t.UN/6fl 'uo!•.eJl.Ua0UOO

E-•70

0 0 C) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 •WN/Bfl 'uop, e•,uaouo9 00o

o

o

£CUN/6rl 'uo!leJl.ueouoo

E-19oo

o

o

oo

o 0
oo

o o

oo

oo

o

s UJN/6rl

'uo!].eJ:].usouoo

E-20ooo o o

oo

oo

oo

o o

oo

oo

£LUN/Gd 'uo!•.eJ•.UeOUOO

00

E-21o

o o o o o co •o

o o

o o

o o

oo cLUN/6d uo!•.eJ•.UeOUO•) o o o o o c0 o o

•LUN/6rt 'uo!•,eJ•.USOUO0

E-2200

0

0 0 0 0 0 0 0 0 0 0 0 CO (.0 • • •LUN/6fl 'uo!le•luaouoo0

00

0

00

0

0

0

0 0 0 0 0 0 0 0 0 0 0 CO • • '•

• uJ N/6fl uo!le.q.ua0uoo00o

E-250

0 0 0 0 0 0 0 0 0 0 0 (D 0 00

00

00

00

0

0

0 o o

o
• 0

o

oo

oo

o

o

o

E-26o o

o o

o o

oo

o o

oo

B-270

00

00

00

0
• 00

00

0 0

0

0

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 @4 0 CO (.(3 • • •WN/6rl 'uop, eJlu:aouoo 0 O

0

00

00

00

0

0

00

00

00

00

O O O O O O O O O O O O (;;O (.O • • O O

• LU N/6fl 'uo!•.e.q.uaouoo

E-280

0 0 0 0 0 0 0 0 0 00

00

00

00

00

00 0 0 0 0 0 0 0 0 0 0 0 0 CO (O '•- £LUN/Bfl 'uo!:l.eJ•.uaouoo sLUN/6fl

'uo!•.eJ•.UaOUOD

E-2900

00

0

00

•

tu NI6d 'uo!•.eJ],ueouo3 00£LU N/6d 'uo!],eJ],ueouoo

E-300

0 0 0 0 0 0 0 0 0 0 0 0 00

00

00

00

oo

oo

oo o o

oo

oo

o o o o o o o o o o o o o co r,..0 •- c• •mN/6fl 'uo!leJ•.Ua0U0O

•mN/fid

'uo!•.eJ•.ue0uo9

oo

o o

oo

oo

E-3l00

00

00

00

00

0

00 0

0 0 0 0 0 0 0 0 0 0 •LU N/Bd 'uo!•,e•lueouooTHIS PAGE

INTENTIONALLY LEFT

BLANKAPPENDIX F MAIN STACK

DAILY

AVERAGE HG CONCENTRATIONSThe following

graphs display

the daily averaged

mercury

monitor

data collected

at the stack d,uring the test program

listed by date. All data have been corrected

and are presented

on a gtg/Nm' basis. For days with a raw-mill-off

condition,

the raw-mill-on

and raw-mill-off

averages were separated.

Error bars show one standard

deviation.

t::-i4oo] %

3501- l •c• 300 • 250

[] Total Hg [] Elemental

Hg EERC JK30416 CDR

200 150 100 50 No Testing 8-Apt

No Testing 9-Apr

No

No Testing Testing 10-Apr 11 -Apr Condition, date

No Testing 12-Apt

Raw Mill On 13-Apr

Raw Mill On 14-Apr

3500 EERC JK304 7. CDR 3000 •2500 2000 500
m 1000 0 [] Total Hg [] Elemental

Hg

tOn15-Apr • Raw R Raw R• Raw R•, Raw Plant Mill I•' Mill M Mill M Mill Offline frill On, ( On O On C _•Onpro-A 16-Apr 17-Apr

18-Apr

19-Apt

21-Apr Condition, date

F-23500 3000 2500 2000 1500. 1000 5000 EERC JK30418. CDR --liE] Total Hg [] Elemental

Hg

Mill Mill

Mill On On

On 22-Apt 23-Apr

24-Apr

Raw Mill On 25-Apr

On 26-Apr

27-Apt Condition, Date

4000 EERC JK30419. CDR 3500 3000 2500 2000 1500 1000 5000 Raw

Raw Mill Mill On Off 29-Apr

[] Total Hg [] Elemental

Hg

Raw Mill Mill On Off 30-Apr 1-May Raw Mill Mill On Off

On 2-May 3-May Condition, date Raw Mill Off 5-May6000 5OOO--- 4000 3000 2000 1000 ---[ i-q Total Hg [] Elemental

Hg

Mill Mill •! • • Mill

II Mill On Off On

•f On 6-May 7-May

8-May

9-May

10-May

11-May

12-May Condition,date

400. EERC JK30421. CDR 350 300 250• 200 150- 100- 50- Raw On 13-May L [] Total Hg [] Elemental

Hg

No Testing 14-May No Testing 15-May

No

No Testing Testing 16-May 17-May Condition, date

No Testing 18-May

No Testing 19-May

F-4THIS PAGE

INTENTIONALLY LEFT

BLANKAPPENDIX G NATIVE MERCURY CAPTURE STATISTICAL EVALUATION AND

SUMMARY OF MM VARIANCESUMMARY OF MM VARIANCE
The following

analysis

is intended

to evaluate

the variance

of the mercury

monitor

(MM) measurement data and determine

1) if the magnitude

of the standard

deviation

is considered statistically and practically

significant

and 2) if the standard

deviation

is consistent

from run to run. First is determined

whether

the data come from a normal distribution.

Next a comparison

of the magnitude

of the standard

deviation

and the average

measurement

is made followed

by a statistical comparison

of the varlances.

All data are m gg/Nm

corrected

to 7% oxygen on a dry basis. In order to understand

whether

the standard

deviation

from each of the steady state periods is consistent,

it must be first known whether

the MM data are considered

to be derived

from a normal distribution.

Some of the data sets while the raw mill is off can be considered

to be from a normal distribution,

but others cannot because

there is often extra weight on one of the tails of the distribution.

Figure G-1 shows the results of the normality

test of Run Period 1, while Figure G-2 shows the corresponding

histogram

with a normality

curve superimposed.

If the data on Figure G-1 follow the plotted straight

line perfectly,

the data are considered

normal.

The probability plot data in some cases follow a straight line, but typically

fall off at the tails. ThePValue of 0.029 (<0.05) derived

from the Anderson-Darling

normality

test indicates

that the data are considered

not normal at the 95% confidence

level. This exercise

was repeated

for all of the run periods.

For the data sets with the raw mill on, data from three of the thirteen periods can be considered

to be from a normal distribution.

When the raw-mill-off

data is looked at, only one of the twelve data sets can be considered

to be normal. It should be noted that many of the raw-mill-off

data sets had very few data points and the accuracy

of the normality

test decreases

with decreasing

data points. Additionally,

some of the distributions

are close to normal and may be considered

normal if some outlier data points
are thrown out. However,

one of the statistical

tests described

in the next section used to evaluate the standard

deviation

can be used with nonnormal

data, so the data sets were not modified

for the analysis.

G-1EERC JK30450 CDF4 Probability Plot of 1 Normal
Mean 290. 3 st. D•. so.82 /•" N tgs -./-.•" P-Value 0.029

100 150 200 250 300 350 400 450 Mercury Concentration,

#gl N rn3 Figure G- 1. Normal probability

plot of the mn period

data. Histogram (with normal curve) of 1

EERC JK304.51. CDR 35- 30- 25- 20- 15- 10-5-0 200

240 Mean 290.3 St. Dev. 50.82 /"-• N 195

280 320

360

400 Mercury Concentration,

•g/Nm 3 Figure G-2. Histogram

of the run period

data with a normal curve.

G-2Evaluation of the variance

of the data can be accomplished

by comparing

the standard deviation to the mean. While there is not a good statistical

test to evaluate

this, practical experience with MMs, mercury

measurements,

and emission

limits can be used to understand what the variation

might mean for emission

limits and control

strategies.

For a normal distribution, 99.74%

of the data points are expected

to fall within _+3 standard

deviations

of the
mean. In the case of Run Period 13, the data were found to be normally

distributed

with an average of 328 •ug/Nm 3 and a standard

deviation

of 48. Evaluating

the data range at _+3 standard deviations shows that 99.74%

of the data points will fall between

184 and 472 ug/Nm 3. The magnitude of the range is very close to the magnitude

of the average,

and the upper limit is 2.5 times greater than the lower limit. Therefore,

from a practical

evaluation

standpoint,

the variation seems very significant. Run Period 13 can be used as a benchmark

to evaluate

the variance

of the other run data. Figures G-3 and G-4 depict the 95% confidence

intervals

of the standard

deviations

calculated for each of the run periods.

Figure G-3 shows the calculated

standard

deviations

with the raw mill on, and Figure G-4 shows the standard

deviations

with the raw mill off. The graph shows that the standard

deviations

of each run period range from about 30 to 130 p,g/Nm 3. The corresponding 95% confidence

intervals

do not overlap

in many cases, indicating

that the variation is changing

from run period to run period. Two tests were used to determine

whether the standard

deviations

from run period to run period were statistically

different.

Bartlett's

test and Levene's

test are two common

statistical

tests to determine

whether

multiple

data sets have equal variances.

Bartlett's

test can be used when the data are known to come from a normal distribution. Levene's

test can be used on nonnormal

but continuous

data sets. Since many of the data sets were shown to be nonnormal,

Levene's

test is probably

the better indicator.

The results of both tests are shown in Figures G-3 and G-4. Both tests on both graphs yielded P-Values

of 0.000, meaning

that at least standard

deviation

is statistically

different

than the others. Further evaluating

the raw mill on data and using Run Period 13 as the benchmark,

it is shown that the confidence

interval

for the standard

deviation

is similar to Run 13 on the remaining runs. The magnitude

of the standard

deviation

varies significantly

on several runs, and the confidence

intervals

do not overlap

for many of the runs. The raw-mill-off

data shows increased variability

over the raw-mill-on

data. Much of this can be attributed

to a low number of data points and a high level of variability

when high concentrations

of mercury

are measured. The noted variation

is either caused by the variation

of mercury

levels in the plant or measurement problems

with the MM. A RATA will determine

whether

the average

mercury level over time is being accurately

measured

by the MM. A gauge R&R study would be needed to determine

if the point-to-point

variation

is caused by the measurement

system or the process.

G-313"2"3"4"5"6"7"8"9" EERC JK30453 CDR Test for Equal Variances

with Raw Mill On for :•3 Run Peri,•ds

• Bartlett's Test
• Test Statistic 668.32 P -Value

0.000 Lev ene's Test Test S•a•c

36.73 P-Value 0.000

20 40 60 80 100 120 140 95% Bonferroni

confidence

intervals for st devs.; unit is Hg conc. in pg/Nm 3. Figure G-3. Test for equal variances

with raw mill on for 13 run periods

14 15 16" 17" 18" 19" 20" 21 22 23 24 25" EERC JK30452. CDF• Test for Equal Variances

with Raw Mill Off for 12 Run Periods

• Bartle•s Test

95% Test S•t•c 839.37 P-Value 0.000 Levene's Test Test Statistic

36.53 P-Value 0.000

0 1000 2000 3000 4000 5000 6000 Bonferroni confidence

intervals for st devs,; unit is Hg conc, in pg/Nm 3, Figure G-4. Test for equal variances

with raw mill off for 12 mn periods.

G-4To

determine

if there is significant

native mercury

capture

in the baghouse,

the inlet and outlet CMM data were analyzed

when no carbon injection

or other mercury

capture

technique
was being tested. The periods

analyzed

were either baseline

runs or start-up

conditions

before injection. The percent

mercury

removal

was calculated

for each of the 11 baseline

or startup conditions. The data were then compared

to zero (representing

no native capture)

using aonesample t-test. The MINITAB

output from the test is shown below. The average

mercury

removal for the periods

was 1.0% with a standard

deviation

on 16.6%. The 95% confidence

interval ranges from about -10% to 12%. The confidence

interval crosses zero and, therefore,

cannot be proven to be different

from zero. The p-value

of 0.846 is greater than 0.05 and, therefore, indicates that we cannot prove the average

native capture is different

from zero. A box plot of the data is also shown below, along with a more detailed

explanation

of the test method. One-Sample T: % Removal Test of mu 0 vs. not 0
Variable N Mean

St. Dev.

SE Mean

95% CI

T P % Removal

11 1.00000

16.59187

5.00264

(-10.14657,

12.14657)

0.20 0.846

EERC JK304,.54. CDR Box Plot of °/o Removal (with Ho and 95% t-confidence

interval for the mean)

Ho

-20 10

0

10

20

30

40 % Removal

G-5Stat

> Basic Statistics

> 1-Sample

t Performs a one sample t-test or t-confidence

interval for the mean. Use l-Sample

to compute

a confidence

interval and perform

a hypothesis

test of the mean when the population

standard

deviation,

•, is unknown.

For a two-tailed

one-sample

t, H,,: !u •t., versus H,: la • •, where iu is the population

mean and •t, is the hypothesized

population

mean. The confidence

interval and t-value calculations

are shown below

Lower Confidence

Limit Upper

Confidence

Limit S S t-value 2 + t-value

value from student's

table for •/2 and (n-l) degrees

of freedom
s sample std. deviation n sample size
x sample mean o• alpha risk X--/.10 tWhere: xbar is the sample mean n is the sample size. uo is the target mean. s is the sample standard

deviation.

G-6THIS PAGE

INTENTIONALLY LEFT

BLANKAPPENDIX H CALCULATION OF A MASS

WEIGHED POTENTIAL ANNUAL

REMOVAL EFFICIENCYA

mass weighted

estimation

of the potential

annual removal

efficiency

based on Tekran mercury monitor

(MM) measurements

made at the stack was calculated

using the information given in Table H-I.
Table H-1. Calculation

of a Mass Weighted

Potential

Annual

Removal

Efficiency Raw-Mill-On Annual Run Time Raw-Mill-Off Annual Run Time Average Raw-Mill-On

Hg Emission,

no Hg control Average Raw-Mill-Off

Hg Emission,

no Hg control Annualized Weighted

Average

Hg Emission,

no Hg control Estimated Hg Removal

Efficiency,

raw mill on Estimated Hg Removal

Efficiency,

raw mill off Estimated Raw-Mill-On

Hg Emission,

with control Estimated Raw-Mill-Off

Hg emission,

with control Annualized Weighted

Average

Hg Emission,

with control

85% 15% 408 gg/Nm 3 2254 ,ttg/Nm 3 685 ,ttg/Nm 3 90% 63% 41 gg/Nm 3 834 ,ug/Nm 3 160 •.tg/Nm 3 Calculating the percent reduction

based on the annualized

weighted

Hg emission

yields a value of 77% reduction. The values were determined

as described

below: Average raw-mill-on

and raw-mill-off

emission

values are taken from the MM data from April 15 through

May 10, 2007. Annualized weighted

average

Hg emission,

no Hg control

(raw-mill-on

annual run time*raw-mill-on Hg emission,

no Hg control)

+ (raw-mill-off

annual runtime*rawmill-off Hg emission,

no Hg control): (0.85*408btg/Nm 3) + (0.15*2254,ug,q',,lm

3) 685gg/Nm

3 Estimated Hg removal

efficiency,

raw mill on was taken from Figure 10. Estimated Hg removal

efficiency,

raw mill off was taken from an average

value taken from Figures

12 and 13 for removal

efficiency

at 5 lb/Macf.

Average

value of 70% and 55% 63%. Estimated raw mill on Hg emission,

with control

average

raw mill on Hg emission,

no control*( estimated

Hg removal

efficiency,

raw mill on) 408 btg/Nm 3 * 0.90) 41 ,ttg/Nm Estimated raw-mill-off

Hg emission,

with control

average

raw mill off Hg emission, with control'*(

estimated

Hg removal

efficiency,

raw mill off)

H-12254 ,ttg/Nm 3 * 0.63) 834 ,ug/Nm Annualized weighted

average

Hg emission,

with control

(raw mill on annual mn time
raw mill on Hg emission,

with control)

+ (raw mill off annual mn time * raw-mill-off Hg emission,

with control) (0.85"41 btg/Nm •) + (0.15 * 834 btg/'Nm 3) 160 btg/Nm 3 Percent reduction

based on the annualized

weighted

Hg emission

(annualized weighted average

Hg emission,

with control/annualized

weighted

average

Hg emission,
no Hg control) 1- ( 160 btg/Nm3/685

,ug/Nm 3) 77%

H-2