The Cannel Coal Industry of Kentucky

Transcription

The Cannel Coal Industry of Kentucky
Energeia Home
Vol. 7, No. 1, 1996
The Cannel Coal Industry of
Kentucky: A Brief History of
Resource Development and Depletion
James C. Hower, Center for Applied Energy Research
INTRODUCTION
The mining of cannel coal was a small, but prestigious, component of coal production
of Kentucky in the 1800’s and early 1900’s. Cannel coal sold for about $2.50/ton (at the
mine) at a time when bituminous coal sold for less than $1.00/ton. Kentucky cannel
coals were marketed throughout the United States and Canada, as well as to Europe
and South America. Perhaps the most unusual marketing of Kentucky cannel occurred
at the 1893 Columbian Exposition at the Chicago World’s Fair where a 23 foot by 27 foot
cannel arch was constructed, modeled after the Arc de Triomphe.
Cannel coal was retorted into liquid fuel, gasified as an enricher of municipal gas
supplies, and distilled as a feedstock for the production of chemicals. Each peak in
usage was subsequently tempered by a discovery of cheaper sources of liquid
hydrocarbons.
The production of cannel, as with any mineral commodity, was at the mercy of market
demands and available transportation. Cannel coal, more than banded bituminous
coal, occurs in relatively limited areas, leading to the rapid exhaustion of commercial
deposits as well as the failed attempts of investors to develop deposits that did not
attain commercial size. This history of the Kentucky cannel industry provides a view
of a limited resource, in many cases, mined to exhaustion, with a rather specialized
market. In some respects, the history of the boom and bust years of the cannel industry
is similar to the development of the coal industry on the whole. The latter’s resources
are not as limited but they are, nevertheless, exhaustible. Furthermore, without a
market and available transportation to get the coal from the mine to market, the
resource will remain
unmined.
Brief histories of two
of the more important
deposits serve to illustrate the history of the
repeated rise and fall of
the cannel coal industry. The Breckenridge
deposit in Hancock
County, Western Kentucky, and the Morgan
County deposits, Eastern Kentucky, will serve
as mirrors on an industry that was important
in its own right but,
overall, was obscured by
the larger bituminous
mining industry.
CASE HISTORIES
Breckenridge
The Breckenridge cannel coal, from
southern Hancock County in Western
Kentucky, ranks as Kentucky’s most
famous cannel. Owing to its outstanding quality, which surpassed that of the
Scottish Torbanehill cannels, it is still
among the best known cannels in the
(continued, page 2)
Evolution of
PYROGRAF IIITM:
Process Produces
Vapor-Grown
Carbon Fibers
Using Coal
Bob Alig
Applied Sciences, Inc.
Hydrogen sulfide has made it possible
to produce vapor grown carbon fiber in
practical quantities. Coal could
eliminate the need for handling toxic
Hydrogen sulfide at an acceptable
price. Furthermore, this could potentially resolve emission problems and
transform high-sulfur coal into a very
desirable commodity.
Introduction
A miner returning home from the coal mine, photo by
Russell Lee, University of Kentucky Photographic Archives
The basic process for producing vapor
grown carbon fibers was developed by
Dr. Gary Tibbetts at the General Motors
NAO Research Labs and described in
ENERGEIA, Vol. 1, No. 4, 1990. In this
process, an organometallic compound
containing iron is injected into a
hydrocarbon vapor at temperatures
above 1000 °C. The fibers lengthen and
thicken as they move through the
reactor with the gas stream and col(continued, page 3)
Cannel Coal, (continued)
world. Local legend traces the discovery
of the deposit to two hunters who
found the cannel at the outcrop and
proceeded to build a cabin and fireplace
with the coal. The first local use of
cannel as a building stone failed.
cannel as a fireplace coal. The mine site
is now a private hunting club.
Morgan County
In the second decade of the 20th
century, Kentucky was considered to be
the premier cannel-producing state.
Morgan County led Kentucky with
production surpassing the total of any
other state, probably surpassing the
production from the Breckenridge
mines (which, pre-dating Kentucky
Department of Mines and Minerals
records, is inaccurately known).
Completion of the link was delayed by
the 1899 Kentucky River floods that
washed away the rail bridge. A rail link
to Morehead eventually served operations on the north side of the county.
The Kentucky Block Cannel Coal Co.
was the largest producer, generally
producing 5-10 times the cannel as its
nearest competitor. The company also
developed oil and gas wells on its
Cannel City property in southern
Morgan County.
The development of the Breckenridge
deposit dates to at least 1837 when it was
sold for the use of Ohio River steamers at
a price equivalent to $2.50/ton. In the
1850’s, the Breckenridge deposit was
The principal cannel coal mined,
developed first as an exportable commodmarketed as the Pluto cannel, and a
In 1892, however, Morgan County was
ity and, later, as a source of liquid fuel. In
thinner cannel were marketed as
remote and the cannel resources were
the early 1850’s, the cannel was sold for
domestic fuel, gas enrichers, and for the
totally undeveloped. Lacking, also, was
up to $15/ton in New York and London
production of cannel-oil by-products.
transportation. Morgan County is on
for use as a gas enricher. Up to 10,000
During the World War I era, the
the Licking River, and did not have the
tons/month were shipped to England,
chemical industry, which had become
railroad access of the Big Sandy,
doubling as ballast for the ships. The
increasingly dependant upon a crudeexport market
oil feedstock, faced
ended in about 1856
wartime shortages.
with the construcCannel oil and coal
tion of 30 retorts
tars from coking were
for coal oil refining.
two of the alternative
The Breckenridge
feedstocks used.
Coal & Oil Company
Postwar industrial
operation was one
growth maintained
of 55 coal-oil compathe demand for
nies operating in
cannel, leading to
the United States
then-record producin 1860. The discovtion in Morgan
ery of petroleum in
County in 1920. The
Western Pennsylvacannel boom colnia the previous
lapsed in 1921,
year and the
production decreasing
subsequent decline
by an order of
in oil prices to
magnitude, as the
$0.52/barrel in 1861
early development of
Map indicates Kentucky cannel deposits discussed. Dotted lines refer to the
killed the coal-oil
the Persian Gulf oil
Eastern
and
Western
Kentucky
coal
field
boundaries.
industry. Most of
fields and the domesthe retorts in the US,
tic oil transportation
Cumberland, or the Kentucky River
many of which had been based on
networks reduced the desirability of
valleys, all sites of earlier mining
Breckenridge cannel, were converted to
using a solid fuel to produce a liquid
development. The nearest railroad, the
crude-oil refining.
product.
Newport News and Mississippi Valley,
Mining resumed in the 1880’s and
A second boom in production followed
was at Morehead, Rowan County,
markets were found throughout the
World War II. In the face of a rapid rise
requiring an 18-20 mile rail extension.
United States and as far away as Nova
in oil prices fueled by the increased
Scotia and Chile. The revival did not
Production was anticipated by 1894 but
transportation and industrial demands,
last as the reserves were depleted to the
“. . . the building of the necessary
the US government funded shale- and
point where the mining production fell
railroad, the prospects for which were
coal-conversion projects in the late
to 300-400 tons/month in 1896, the
so promising early in the year, failed
1940’s. Again, the development of
equivalent of one day’s production in
through unexpected difficulties
Persian Gulf oil fields, offshore petro1887. Underground mining ended in
(Norwood and Grider, 1894, KDMM
leum resources in the Gulf of Mexico,
November 1898, a victim of the market
report).” Morgan County finally
and improved oil transportation
disruptions caused by the Spanishentered commercial production in 1901
networks effectively killed any hope of
American War, armed conflict with a
with the Caney Cannel mine (Biggstaff
developing a synthetic-fuel industry.
major customer never being good for
Cannel Coal Co.) and the Kentucky
The most recent cannel mining in
business. John Taulbee from Morgan
Block Cannel mine (Kentucky Block
Morgan County, with the intended
County owned the deposit from about
Cannel Coal Co., New York City). The
market being home heating in Ireland,
1904 to his death in the early 1970’s. He
final rail connection was the Ohio and
was abandoned after mining a few
attempted to mine the deposit but was
Kentucky Railroad covering 27 miles
hundred tons. For the first time since
unsuccessful. The next owner, John
between Caney (Morgan County) and
the beginning of cannel mining,
Corder, did surface mine the remains of
Jackson (Breathitt County) on the
Morgan County produced no coal,
the underground works in 1977, with
Kentucky River where it connected
cannel or bituminous, in 1994.
his Warm Glow Coal Co. marketing the
with the Lexington & Eastern Railroad.
(continued, page 3)
2
Cannel Coal, (continued)
PYROGRAF IIITM, (continued)
SUMMARY
lected as they exit. Precise control of the
hydrocarbon and ferrocene or iron
pentacarbonyl flow rates is necessary to
achieve optimum growth. This fiber was
known as PYROGRAF IITM. However,
the process was non-productive; the iron
catalyst did not grow filaments profusely
enough to be a practical continuous reactor. From these initial developments at
General Motors, a joint venture collaboration was entered into with Applied
Sciences, Inc. in 1992 for further development and manufacture.
The cannel industry in Kentucky
garnered prestige far beyond its
contribution to the total coal production of the commonwealth. Cannel
production compared with bituminous
production peaked at 2.2% in 1895. By
the time Morgan County came into full
production in 1902, cannel production
was only 1% of bituminous production.
Cannel filled a niche market as a
specialty fuel. When those markets
were serviced by cheaper, more
convenient fuels, the market for cannel
diminished. The coming of pulverizedfuel combustion, as opposed to stokerfired combustion that could handle
larger particle sizes, placed
greater value on the easier-pulverized
bituminous coals, further displacing the
extraordinarily hard, although higher
heating value, cannel coals.
Despite the dreams of investors, who
still, at times when synthetic fuels may
be approaching economic viability,
hope to exploit cannels for their
inherent high retortable oil content,
cannel can now be best described as a
novelty fuel. Considering the limited
extent of cannel deposits and the nearexhaustion of the best deposits, the
absence of a market for cannel in the
utility sector, and the persistent future
development of synthetic fuels (in
which cannel, for the first reason cited,
would not play a significant role),
cannel use is not likely to expand
beyond its current domestic markets.
Although there was only a limited
production of cannel, lessons from its
history can be applied to the coal
industry as a whole. Cannel was a
desired commodity, leading companies
to develop resources which, owing to
the limited nature of the deposits, were
not able to support the market demand
for the product. Prior to that point, the
cannel could not be developed before
rail transportation from the mine to the
market was in place. Ultimately, cannel
was displaced by cheaper, more easily
transported fuels, losing the extensive
market it had gathered through the late
1800’s and early 1900’s.
A version of this article first appeared in
“Uncertain and treacherous: the cannel coal
industry in Kentucky,” which appeared
in the journal, Nonrenewable Resources,
v. 4, p. 310-324, 1995.
Dr. Hower is the senior coal petrographer at the
CAER. He has been with the center since 1978.
Sulfur Innovation
A breakthrough occurred when it was
found that sulfur was vital to fiber formation. Adding hydrogen sulfide (H 2S) at
an equimolar level with the iron catalyst,
vastly increases the filament formation as
shown in Figure 1. This made it possible
to proceed and develop the concept of a
continuous reactor. The sparse fiber in
the photo without sulfur clearly illustrates
the need for sulfur. We believe that the
sulfur becomes involved as a eutectic and
is incorporated in the fiber by being
adsorbed onto the catalyst, and subsequently overcoated with graphite. Furthermore, excess sulfur up to 12 times the
S/Fe molar ratio still produces good fiber,
but gradually develops a shorter, jagged
structure at higher ratios.
PYROGRAF IIITM
Figure 2 shows scanning electron micrographs of vapor grown carbon fiber made
using sulfur in comparison with typical
commercial carbon fibers. The diameter
of this fiber, known as PYROGRAF IIITM,
generally averages 0.2µ as produced,
while commercial fibers are 8µ in diameter. Due to the random distribution of
the catalyst during fiber formation, the
fibers become entangled during growth
and are not in continuous lengths like
commercial fibers. The length/diameter
ratio for PYROGRAF IIITM ranges from
40 to 200. Due to the process, the material
can be highly graphitized as it is made
as shown in Table 1, which is similar or
higher than heat treated, commercial
carbon fibers.
10µm
a
a
10µm
b
Figure 2. Typical commercial fibers (a) in
comparison with vapor grown carbon fiber
using sulfur (b).
b
Table 1. X-Ray Diffraction Analysis
Heat
Fiber
Treat (°C) Type
c
4µm
Figure 1. Effect of H2S on fiber growth. (a)
no H 2S flow (b) at equimolar levels (c) at
17:1 ratio.
3
D-Spacing gp
(nm)
(%)
As-grown VGCF
1300
ex-PAN
As-grown Coal &
Methane
As-grown Coal only
2500
ex-PAN
2500
VGCF
As-grown PYROGRAFIII
-P-120
.34490
.354
.3459
----
.3459
.342
.3377
.3385
.3378
-23
73
64
72
(continued, page 4)
PYROGRAF IIITM, (continued)
Hydrogen sulfide
Most of the PYROGRAF IIITM made to
date has used laboratory grade methane
as a hydrocarbon source to assure reproducible results. Since one reactor can
now produce almost a pound per hour,
natural gas is frequently used and the
hydrocarbon variations do not affect the
output. A pound of fiber made with laboratory grade methane adds $70 to the
cost as compared to $0.44 for natural gas.
Although the addition of H2S was instrumental in achieving this improvement, it
was used with great reluctance. Hydrogen sulfide is expensive, highly corrosive, flammable, and its toxicity is commensurate with hydrogen cyanide. Suppliers are hesitant to ship the material
and prefer to ship H2S that has been
diluted in CH4 to the 1 to 3% level at
an astronomical cost.
Since coal contains many compounds of
sulfur and all may not participate in the
reaction, a 1.6 ratio was chosen that was
higher than the usual “control” formulations with a 1.0 H2S/Fe[CO]5 molar
ratio. Ohio #8 Coal from CONSOL Inc.,
at 4.71% total sulfur and 46.6% total
carbon, was pulverized to less than 63µ.
Trial 2 was to test the hypothesis that
coal could be the only supply of the
hydrocarbon and sulfur, and produce
vapor grown carbon fiber. The pulverized coal was carried into the reactor
with a non-hydrocarbon carrier,
hydrogen. Upper Freeport Seam coal
was obtained from Kaiser Engrs. with
2.5% total sulfur and an estimated 65%
carbon content. In this trial designed to
run without methane dilution, the
molar sulfur/catalyst ratio was 4.5. The
formulations are as follows in Table 2.
Coal trials
A reactor that normally uses a feedstock
mixture of 99.9% pure methane was converted to accommodate the use of coal.
For catalyst, helium was bubbled through
liquid iron pentacarbonyl to provide Fe
particles for the 1100 °C reactor. A screw
type apparatus was assembled to feed the
coal into the injection stream and a carrier
gas transported the coal and catalyst into
the reactor.
Two types of coal trials were made. The
first was to test the hypothesis that
sulfur-bearing coal can replace H2S as
the source of sulfur in the reaction. In
this case, coal and methane were used
as the hydrocarbon feedstock. Methane
was the carrier gas and calculated to
maintain a 1.6 molar sulfur/iron ratio.
Figure 3. Coal replacing hydrogen sulfide Trial 1
Control and Basic Formulations*
Coal
This suggests that a fossil fuel such as
high sulfur coal may be especially
appropriate for consideration since
millions of tons of high sulfur coal are
no longer being mined due to the 1990
Clean Air Act Amendment. As an
example, Ohio coal production has
fallen from 55 million tons in 1970 to 33
million tons in 1990 and projected to
drop to 17 millions tons. Furthermore,
coal would have a tremendous effect on
the eventual price of the fiber. The
hydrocarbon is the most expensive cost
item, followed by the electric oven
energy and the catalyst. Although the
energy consumption and output
capabilities are not yet optimized for a
total cost picture, the formulations
indicate that the hydrocarbon in coal
could potentially cost ten times less
than natural gas and totally eliminate
the price and hazards of H2S.
10µm
Control Trial 1
Methane
Coal
Sulfur
Hydrogen
Helium
Fe(CO)5
96.90
None
0.47
None
0.96
1.68
87.58
9.33
0.44
None
0.96
1.69
Trial 2
None
80.68
2.02
13.30
1.45
2.55
* Formulations are in percent by weight
Results
In Trial 1, with coal, methane, and no
H2S, the photomicrograph in Figure 3
shows very good growth and confirms
that the sulfur contained in the coal plays
an active role in the catalytic process, and
can potentially replace the need for using
H2S in the reaction. The sulfur content in
coal is well beyond the optimum amount
for the formation of carbon fibers. Nevertheless, this wide range of sulfur acceptability leads to the consideration of high
sulfur coal. In spite of its problems for
other uses, it may be a unique essential
asset for the production of vapor grown
carbon fiber.
In Trial 2, coal is the only source of both
hydrocarbon and sulfur and an SEM
photomicrograph is shown in Figure 4.
There is good, but shorter fiber formation with a fair amount of soot and/or
ash. Nevertheless, these results support
the conclusion that the inherent carbon
in coal is actively pyrolyzed to products
which participate in the catalytic fiber
nucleation and growth process.
Exhaust Emissions
Photomicrographs are the initial
estimate of fiber formation. However,
X-ray diffraction estimates the graphitic
ordering for assuring the quality of the
4
10µm
Figure 4. Coal as sole hydrocarbon source Trial 2
fiber’s strength and conductivity. Table
1 shows that the fiber samples from coal
Trials 1 and 2 have a graphitization
index that is typical for low modulus
commercial fiber.
In earlier trials that rely on introducing
H2S into a pure methane feedstock at
equivalent ratios with the catalyst, periodic analyses were made of the exhaust.
To date, sulfur has not been detected in
the exhaust. This could be explained by
the idea that the sulfur dissolves in such
large amounts that it melts the iron catalyst and thus stays with the catalyst at the
base of the fiber. How much sulfur can be
dissolved as the sulfur increases is unknown. A packed column gas chromatograph (GC) with thermal conductivity
detector was used to estimate the composition of the exhaust gases of a series of
coal trials when the sulfur was running at
4.5 times the usual amount (Trial 2) and
the presence of sulfur was not detected.
This instrument does not have the sensitivity to measure nitrogen or sulfur compounds below about 0.1-1 %. Future work
is needed with a capillary column GC
with dedicated nitrogen and sulfur
detectors.
Residual Ash
There is a wide variation in the organic
and ash content in coal. Trials to date
indicate that their presence does not
inhibit the growth of a carbon fiber.
Furthermore, there is no indication that
(Continued, page 5)
COMMENTARY
The Difference Between Informing
and Educating
Richard Lawson
President National Mining Association
There is no other nation that surpasses the U.S. in terms of care for the environ-
ment, and we can support this by showing nearly $1.3 trillion in expenditures for
environmental protection activity since 1980.
“Tell the miners from me that I shall promote their interests to the utmost of my
ability; because their prosperity is the prosperity of the nation, and we shall
prove in a very few short years that we are indeed the treasury of the world.”
These words of Abraham Lincoln’s were transmitted to a westward-bound
Cabinet secretary on the afternoon of April 14, 1865, one of the last official
statements made by the president before he left for Ford’s Theatre. They illustrate the great perceptive insight and depth of understanding that Lincoln
brought to so many issues of his time.
Undoubtedly, were Lincoln to be magically transported to the modern era, he
would not be surprised by the critical position the products of mining have come
to occupy in our society. There is no question that mining is inexorably linked,
not only in broad terms to our nation’s prosperity, but specifically to our daily
lives as citizens of the United States and the world.
This is a great and immeasurable responsibility which every component of our
industry - from miner to corporate CEO - takes seriously. At the same time, mining
companies also have long recognized another important aspect of their public
obligation: that with the right of mineral and coal extraction comes the duty of
restoring the land and operating in an environmentally responsible manner.
Our most extreme critics would have you believe otherwise. They are quick to
demand that the mining industry feel ashamed of its environmental track record.
The most severe of these individuals and groups would be satisfied with nothing
less than a cessation of mining activity as we know it. Some others, while willing
to begrudgingly tolerate limited mining, seek regulations and restrictions so
harsh that they border more on the punitive than the practical. Our opponents
have attempted to turn these viewpoints into public opinion and, ultimately,
public policy. In some instances, as we know all too well, they have succeeded,
much to the detriment of our industry and the nation.
Yet, we also know from opinion polls that in spite of this, the general public
overall does not have a negative view of the mining industry and its environmental performance. In fact, most people do not have an opinion at all, either
favorable or unfavorable. What this says, in part, is that we have been doing our
job so quietly and efficiently that the average person simply doesn’t think about
us. But there is also no doubt that we in mining have not done an adequate job
of educating - not simply informing - but educating the public-at-large about our
unmatched productivity, our environmental performance and mining’s importance to everyday life, and to the nation’s security.
Providing information and informing people is an action that, in essence, is
rather benign. It infers that you are making data available; if your target audience wants to assimilate it, fine. If it doesn’t, then it really doesn’t matter how
good your numbers and arguments are.
But education is another process entirely. As the ancient Chinese proverb says,
“Give a man a fish and you feed him for a day. Teach a man to fish and you feed
him for a lifetime.” Fundamentally, educating means providing the tools for
society to differentiate between fact and fiction and to use information to make
intelligent choices.
For these and other reasons, effectively educating constituent audiences about
mining will be a key activity of the National Mining Association for the foresee(Continued, page 6)
5
the ash becomes embedded in the
structure of the fibers during formation
and causes inclusion flaws. This type of
flaw is intolerable in fiber that is only
0.2µ in diameter.
Future Work
The next phase will evaluate the sulfur
content over a wide range of sulfur/catalyst ratios to establish the highest level
that will produce good fiber with no emission problems. In addition, extensive trials will be made to assure that the ash can
be consistently removed from the reactor
during production without buildup in
the reactor. This data will provide the
basis for future projections of coal usage.
Although residual ash is tolerable for some
applications such as rubber or cement, it
could be separated from the coal before
injection or filtered from the fiber during
subsequent pelletization. In practice, the
wide range of sulfur and ash in coal will
most likely mandate a combination with
natural gas to maintain the process balance needed for optimum production.
The role of coal has significant implications not only for coal usage, but also
could develop a fiber price that would
make it possible to consider everyday
applications for carbon fiber in rubber,
cement and plastic composites.
Robert Alig is Senior Research Scientist at
Applied Sciences, Inc., responsible for
production scale-up of vapor grown carbon
fiber. Prior to 1992, he worked on the initial
pilot line at General Motors.
CAER
Goes
Global
on World Wide Web
http://www.caer.uky.edu
The CAER has its own home
page on the World Wid Web! We
have included information on
research, upcoming events,
information services, and
Energeia articles.
Come browse with us.
If you'd like more information on
our Web site, contact Alice Marksberry at
606-257-0308 , e-mail
alice@alpha.caer.uky.edu or
Kathleen Sauer at 606-257-0288, e-mail
sauer@alpha.caer.uky.edu. For question
regarding Energeia, call Marybeth
McAlister at 606-257-0224, e-mail
mcalister@alpha.caer.uky.edu
Commentary, (continued)
able future. And teaching the truth about
our industry’s environmental performance will be a key part of the message.
What the public will hear is this without question, a fundamental reason
the U.S. economy is so competitive is
that our mining industry produces
products so efficiently, productively,
safely and inexpensively. There is no
other nation that surpasses the U.S. in
terms of care for the environment. And
the U.S. mining industry is at the
forefront of that great national
environmental crusade.
This message will be carried in a variety
of forums: the Internet, where NMA
has its own home page; managing
existing educational resources and
creating new ones; and taking advantage of traditional media, publication,
advertising and communications
outlets. Over the long term, our
successful use of these avenues to
educate will result in a sustainable
future, not only for our industry, but
also for America and the world.
A version of this editorial first appeared in
Mining Voice, Volume 1 (5), November/
December 1995.
American Carbon Society Workshop
Wild Dunes Resort,
Isle of Palms,
Charleston,
South Carolina, USA
June 9-12, 1996
The workshop will highlight
the diverse ways in which
carbon materials are used to
prevent and remediate
environmental pollution.
For more information, please
contact:
Dr. Fred Baker
Charleston Research Center,
Westvaco Corporation
P.O. Box 118005
Charleston, SC 29423-8005, U.S.A.
Telephone: (803) 745-3942;
Fax: (803) 745-3742
Energeia is published six times a year by the University of Kentucky's Center for Applied Energy Research (CAER). The publication features aspects of energy resource
development and environmentally related topics. Subscriptions are free and may be requested as follows: Marybeth McAlister, Editor of Energeia, CAER, 3572 Iron
Works Pike, University of Kentucky, Lexington, KY 40511-8433, (606) 257-0224, FAX: (606)-257-0220, Copyright © 1996, University of Kentucky.
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