Project status: Ongoing

P R O J E C T F A C T S H E E T

Development of Activated Carbons

from Coal Combustion By-products
EMS Energy Institute • www.energy.psu.edu
Goal College of Earth & Mineral Sciences • Penn State University

Background
The objective of this research is to develop a cost-
effective process for producing adsorbent materials
from coal combustion by-products, specifically
Approximately 90% of the total US coal production is
unburned carbon.
used in coal-fired units to generate over 55% of the

Team
The EMS Energy Institute is currently working with the
National Energy Technology Laboratory, U.S.
Department of Energy, Consortium for Premium
Carbon Products from Coal, Reliant Energy, Carbon
Plus, Prep Tech, West Materials, Koppers Industries
and Calgon Carbon.
Project Discussion
In this research project, three tasks have been defined:
country’s total electricity. The combustion of over 900
million tons of coal generates annually around 60 million
tons of fly ash.
As coal-fired power plants install low-Nox burners to
reduce plant emissions, the relative percent of unburned
carbon in the plant ash increases. Because the coal-
derived unburned carbon has gone through a devola-
tilization process while in the combustor and contains
over 90% carbon, the unburned carbon is a highly
attractive raw material for the production of activated car-
bons. Also, unburned carbon only requires a one-step
activation process, as compared to the conventional two-
step process that includes a devolatilization of raw mate-
rials, followed by an activation step.

Collect samples from different combustion processes, The implementation of increasingly stringent Clean Air
using a wide range of analytical techniques, to ensure Act Regulations regarding NOx emissions has given way
that the findings can be applied to the different to a drastic rise in the concentration of unburned carbon
combustion technologies used by the power industry. present in fly ash. This has restricted the principal use of
ash in the cement industry, since the carbon present in fly
Investigate several routes for the preparation of activated ash tends to adsorb the air-entrainment agents added to
carbon, including physical activation with different gases, the cement to prevent crack formation and propagation.
such as steam and CO2, at various flow rates and Annually, approximately 6 million tons of carbon-rich ash
temperatures, and chemical activation. are consequently placed in US holding ponds or landfills.
Systematically characterize the properties of the resultant
activated carbons, especially their porous structure and
possible commercial applications.
Completion of this research program will establish a
novel, cost-effective process for the production of
adsorbent materials from unburned carbon. Present
global consumption of activated carbons is over 350,000
tons, and is estimated to rise 7% annually. As a result of
an expanding market for activated carbons, especially in
applications related to environmental protection, new
precursors are being sought.
Results
Samples from different combustion processes are
collected to secure that the findings can be applied to 1000
the different combustion technologies used by the
900
power industry. The samples collected have been
Activated carbon
produced in: (i) pulverized utility boilers, where samples 800
from unburned
were collected from systems retrofitted with low- NOx 700 carbon
Commercial
burners and from units that have been retrofitted with a 600 activated carbon
Selective Non Catalytic Reduction system; (ii) samples
500
collected from an utility cyclone unit equipped with a
beneficiation technology; (iii) class C fly ashes; and (iv) 400

samples from a suspension-fired research boiler (2 MM 300

Btu/hour). 200

The porosity of the unburned carbon samples 100

assembled was characterized by N2 adsorption
isotherms at 77K. The results showed that the surface
areas of the class F fly ash samples from the
2
pulverized utility boilers were between 30-40 m /g,
while the samples from the suspension-fired research
2
boiler had surface areas around 115 m /g. As
expected, the surface areas of the class C ashes have
much higher surface areas than the class F, with
2
values up to 390 m /g.
The activation of the unburned carbon samples was
successfully carried out in a vertical furnace using a
one-step process, that includes simultaneous
carbonization and activation. The activation process
used involves physical activation with steam of the
unburned carbons at temperatures around 850°C for
periods of 1-2 hours. The samples activated for the
longest time (2 hours) present higher BET surface
areas than their counterparts activated for 1 hour. The
one-step steam activation process can effectively
convert unburned carbons with surface areas typically
2 commercial carbons. Activated carbons from fly ash carbon
around 40m /g, into activated carbons with surface
2 can have surface areas as high as 931m /g that is
areas as high as 750 m /g. However, as the activation
time increases, the developing rate of micropore
(<2nm) volume decreases, where micropore volumes
are highly desired in commercial activated carbons.
Therefore, a pretreatment process has been designed
and applied to unburned carbon samples to improve
their reactivity, and therefore, to modify the micropore
0
Surface area, m2/g Micropore surface Iodine number, External surface
area mg/g area, m2/g
Comparison of an Activated Carbon Produced from Unburned
Carbon with a Commercial Carbon.
structure of the resultant activated carbon. All the different
pretreatment conditions studied promote the porosity of
resultant activated carbons, where the surface area
increases ~11-60%. The optimum pretreatment conditions
o
found during the current reporting period are 400 C and 2
hr, where the resultant activated carbon has a surface area
2
of 931m /g, which is comparable to the values reported for
commercial activated carbons.
The produced activated carbons are compared with
2
2
comparable to 966m /g of commercial activated carbons.
Finally, iodine number tests to assess the most suitable
commercial applications of the activated fly ash carbons are
being conducted at our laboratories. Iodine number for the
activated unburned carbon is 836mg/g, indicating that it can
be used for commercial applications like water filtration.

Key Publications
Y. Zhang, Z. Lu, B.N. Shaffer, M.M. Maroto-Valer, J. M. Andrésen, and H.H. Schobert, 2002, Comparison of
Activated Fly Ash Carbons with Conventional Commercial Adsorbent Carbons Proceedings Conference on
Unburned Carbon on Utility Fly Ash, 10.
M.M. Maroto-Valer, Y. Zhang, Z. Lu, A. Jones, J.M. Andrésen, and H.H. Schobert, 2001, Environmental Benefits of
Producing Adsorbent Materials from Unburned Carbon, 2001 International Ash Utilization Symposium, Paper
82Maroto.pdf (CD-ROM publication). (pdf)
M.M. Maroto-Valer, Y. Zhang, Z. Lu, J.M. Andrésen, and H.H. Schobert, 2001, Potential Non-fuel Uses of Unburned
Carbon from Fly Ash for Value Added Carbon Products, Proc. 18th International Pittsburgh Coal Conference, CD,
52-01.pdf. This publication is available in alternative media on request.
Penn State is committed to affirmative action, equal opportunity, and the diversity of its workforce. (May 2002) U. Ed. EMS 03-04