Activated Carbon

Activated Carbon
Joe Choromanski
Ripley Aquariums
Activated Carbon
(Everything I thought I knew but
I was WRONG!)

Joe Choromanski
Ripley Aquariums
1st AQUALITY Symposium, April 2 - 7, 2004, Oceanario de Lisboa, Portugal
Activated Carbon
The use of activated carbon in
marine aquariums has historically
generated fierce debate.
Activated Carbon
Some aquarists believe that
activated carbon is a miraculous, if
not mysterious, magical potion used
to cure all things in the aquatic
environment.
Activated Carbon
Other aquarists feel that activated
carbon is the devil incarnate, sucking
the life force of trace elements,
essential amino acids and other
nutrients out of the aquarium.
Activated Carbon
What got me interested in this exciting topic?
Activated Carbon
What got me interested in this exciting topic?

Charcoal-mellowing refers to a process used to make Tennessee whiskey,
such as Jack Daniel's. The process involves slowly dripping the newly made
whiskey through giant containers hard-packed with 10 feet of sugar maple
charcoal. The process takes ten days, and during this time the whiskey
absorbs the essence of the charcoal, refining the spirit and giving it a unique
flavor and aroma.
Activated Carbon
History of Activated Carbon:
First described used over 3500 years ago
for medicinal purposes (1550 B.C. in an
ancient Egyptian papyrus and later by
Hippocrates and Pliny the Elder)
In the 18th century, crude carbons made
from blood, wood and animals were used
for the purification of liquids.
Activated Carbon
In the 19
th
century, crude AC made from
bone char (powder) was used to de-
colorize sugar (mostly calcium phosphate
with only a small % of carbon).
Early 20
th
century, processes were
developed to steam activated powdered
char for taste and odor removal in water.
Activated Carbon
Granular Activated Carbon with industrial
level steam activation was developed as a
consequence of WWI, for use in gas
masks
Activated Carbon
What is Activated Carbon?
Activated Carbon is a crude form of
graphite and generic term used to
describe a family of carbonaceous
adsorbents possessing a highly crystalline
form and extensively developed internal
pore structure.
Activated Carbon
What is Activated Carbon?
This unique structure of Activated Carbon
produces a very large surface area:

1 lb. of Granular Activated Carbon
produces a surface area of 125 acres
(1 kg = 1,000,000 meters
2
; 1000 m
2
/g)
Activated Carbon
Activated Carbon can be produced from a
wide variety of carbonaceous raw
materials including:

Bituminous Coal
Coconut Shells
Wood
Lignite Coal
Peat, Olive Pits, etc.
Activated Carbon
The choice of raw material has a large
influence on the characteristics and
performance of the AC, each producing
an AC with differing surface areas, total
pore volume, pore radius and pore
volume distribution.
Activated Carbon

Carbon Type Total Pore
Volume (ml/g)
Mean Pore
Radius
(Angstroms)
Surface
Area (m
2
/g)
Coconut Shell 0.5 0.6 10 11 1000-1100
Peat 0.6 0.7 11 12 1000-1275
Bituminous Coal 0.6 0.7 12 14 1000-1150
Bituminous Coal 0.7 0.8 14 16 900-1050
Lignite Coal 0.9 1.0 29 32 900-1050
Peat 1.1 1.2 23 26 600-675
Wood 1.4 1.8 22 - 26 1200-1600
Activated Carbon
Pore Structure
Activated Carbon
Activation
The raw materials are first carbonized via
a controlled heating process at low
temperatures (200 - 300C) in an oxygen-
lean environment which keeps the
material from burning. This process
converts the raw material into a
disordered carbon structure full of tiny
pores.
Activated Carbon
Activation
The carbonized materials are then
activated by steam (or chemical
treatment). Steam activation is carried out
at high temperatures (982C) and the
carbonized materials react with the steam
to form carbon monoxide and hydrogen
which exit as gases leaving behind a
highly porous activated carbon material.
Activated Carbon
RE-Activation
The adsorptive capacity of any AC is
exhausted eventually.
After carbon becomes used up (pore
spaces filled), it can be partially
reactivated w/ high temperature steam
Very expensive but is done in the
municipal drinking water industry
Activated Carbon
AC Production
Activated Carbon
The Three Types/Forms of AC
Powdered Granular
Pelleted / Extruded
Activated Carbon
Activated Carbon Particle Sizing

Mesh
U.S.(ASTME11)
A
Inches
A
mm
B
Inches
B
mm
4 1/4" 6.350 0.187" 4.760
8 1/8" 3.175 0.093" 2.380
10 1/10" 2.540 0.079" 2.000
12 1/12" 2.117 0.066" 1.680
14 1/14" 1.814 0.056" 1.410
16 1/16" 1.588 0.047" 1.190
20 1/20" 1.270 0.033" 0.841
30 1/30" 0.846 0.023" 0.595
40 1/40" 0.635 0.017" 0.420
Activated Carbon
Measuring Adsorptive Properties
Molasses Number / Decolorizing
Efficiency
Higher number, better performance with large
molecule contaminants
Activated Carbon
Measuring Adsorptive Properties*
*None are good indicators of DOC removal
Iodine Number
This test measures very small pores
A high number indicates good performance
on small-sized contaminants
Tannin Value
Tastes & odors; low number good
Butane Activity (formerly CCl
4
)
Vapor phase only
Activated Carbon
Choosing the correct type of AC:

Different purification goals require
different activated carbon properties.
There are >150 types of carbon available

Activated Carbon
Choosing the correct type of AC:
There are no valid theories that allow
selection of the best activated carbon in
any single case without experimentation
(Johnson et al., 1964)
It should be mentioned that the
mechanisms by which activated carbon
removes organic matter from water are
unclear (Spotte, 1984)
Activated Carbon
AQUARIUM USES FOR CARBON:
Dissolved Organic Carbon Removal
Chemotherapeutants
Proteins (yellow color; non-ozonated systems)
Organic acids, carbohydrates, hormones, etc.

Oxidant Removal
Chlorine / Chloramine from drinking water
Ozone byproducts
Activated Carbon
Dissolved Organic Carbon Removal
Activated Carbon removes organic
compounds from water via physical
adsorption
Activated Carbon
What is Adsorption?
Organic molecules bond to the internal
pores of activated carbon
Activated Carbon
What is Adsorption?
Adsorbates are held on the activated
carbon pore wall surface by weak
electrostatic forces (van der Waals
forces)
Activated Carbon
Adsorption is a fight against solubility
(Sigworth and Smith. 1972. Adsorption of Inorganic Compounds by Activated Carbon. JAWWA, 64(6):386-391)
The more soluble a substance, the less
likely it is to be adsorbed.
Variables such as temperature, adsorbate
concentration (lower better) and pH affect
both solubility of the adsorbate and the
adsorption by the activated carbon.
Activated Carbon
The AC surface is non-polar which makes
non-polar organic molecules most readily
adsorbed.
Will not adsorb salts
Will not adsorb alcohols
Presence of biofilms can affect adsorption
Activated Carbon
What about therapeutic Copper?
Not known how copper is removed by
carbon, but it is (can be measured).
Cu has been classified as an element of
low or unknown adsorption potential
(Sigwood & Smith, 1972).
Possibly more easily removed when
complexed with other substances (Sigwood &
Smith, 1972; Keslar, 2002)

Activated Carbon
Trace metals
Some easily removed when in low
concentrations in FW
Any physical adsorption process can
remove trace ions from solution
Depends on the metal (some have good
adsorption potential while others do not)

Activated Carbon
Oxidant Removal
Activated Carbon removes oxidants
(Chlorine & Chloramine) from water via
reactions, not adsorption
Activated Carbon
Oxidant Removal Chlorine (free chlorine HOCL)

Chlorine will oxidize carbon physically
(actually destroys the carbon)
Chlorine can bind w/ surface oxides
Chlorine can react w/ surface & breaks down
to other products (chloride ions)
Reaction fast; never sees pores
Activated Carbon
Oxidant Removal Chloramines (NH
2
Cl, NHCl
2
, & NCl
3
)

A little more difficult that Chlorine
Catalytic oxidation and adsorption
Ammonia initially formed but quickly converts
to N
2
Chloride ions
Activated Carbon
Activated Carbon
Oxidant Removal Filter Design

Smaller particles or powders best (high SA)
Must balance high SA desired with filter
vessel particle retention ability during
filtration and backwash

Activated Carbon
Water Treatment Methods for GAC & PAC
(Diagrams from Calgon Carbon Corporation / Chemviron Carbon)
Activated Carbon
DOC Removal Filter Design

Should follow biological and mechanical
filtration systems.
Should precede disinfection (except when
used to reduce oxidants in mixed systems)

Activated Carbon
PHOSPHATES??

Many aquarists (especially hobbyists)
believe carbon contributes phosphates to
their tanks from carbon acid washing during
production with phosphoric acid.
MYTH No commercial carbons are washed
with phosphoric acid; only HCl and only in
certain applications (adds cost).

Activated Carbon
PHOSPHATES??

MYTH No commercial carbons are washed
with phosphoric acid; only HCl and only in
certain applications (adds cost).
Carbons are acid washed to REMOVE any
remaining phosphorus from carbon (raw
materials used do contain phosphorous)
Can test carbon for P or pH before using.

Activated Carbon
So, whats the best carbon for aquariums?

Depends on the target contaminant and
many, many other variables
In general:
a coal-based carbon (bituminous, not lignite)
Low ash (pH), high in macro & micropores
Harder, less moisture
8 x 30 to 12 x 40 mesh
Acid washed in HCl

Thank you!

Activated Carbon

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