You are on page 1of 10

Cover Story

Activated Carbon:
Fundamentals and
New Applications
Activated carbon sorbents are important tools in water purification and air-pollution control. This
article provides information on the fundamentals of this diverse sorbent and on new applications
for which it is being employed

G
Cabot
Ken Koehlert lobal sustain-
Cabot Corp. ability trends
are creating in-
creased demand
IN BRIEF for purification of air and
ACTIVATED CARBON water, as well as more en-
BASICS vironmentally friendly pro-
cess alternatives. Activated
RAW MATERIALS carbon (AC) sorbents play
ACTIVATION PROCESSES important roles in applica-
tions throughout the chemi-
POST-PROCESSING
cal process industries (CPI).
ADSORPTION These range from traditional 1,000 nm 100 nm
FUNDAMENTALS applications, such as mu- FIGURE 1. These images from a helium-ion microscope show the pore structure of
FACTORS AFFECTING nicipal water purification lignite-based activated carbon
PERFORMANCE and fluegas treatment, to
cutting-edge applications, such as ad- ner. The degree of order varies based on
APPLICATION TYPES
sorbed natural gas storage and double- the starting raw material and thermal his-
BIOGAS PURIFICATION layer capacitors. tory. Graphitic platelets in steam-activated
SEDIMENT REMEDIATION In this article we review the basics of ac- coal are somewhat ordered, while more
tivated carbon, as well as the link between amorphous aromatic structures are found in
activated carbon properties and adsorption chemically activated wood.
performance. In addition, the article provides Randomized bonding creates a highly po-
an overview of two emerging applications for rous structure with numerous cracks, crev-
activated carbon sorbents — biogas purifi- ices and voids between the carbon layers.
cation and sediment remediation. Activated carbon’s molecular size porosity
and the resulting enormous internal surface
Activated carbon basics area make this material extremely effective for
Activated carbon is a highly porous, high- adsorbing a wide range of impurities from liq-
surface-area adsorptive material with a uids and gases. To provide some perspective
largely amorphous structure. It is composed for the internal surface area of activated car-
primarily of aromatic configurations of car- bon, the annual activated carbon production
bon atoms joined by random cross-linkages. of the author's employer has a surface area
Activated carbon differs from another form nearly equal to the total land area on Earth
of carbon — graphite — in that activated (148 million km²). Figure 1 shows two micro-
carbon has sheets or groups of atoms that graphs of the internal structure of steam-ac-
are stacked unevenly in a disorganized man- tivated lignite.
32 CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM JULY 2017
Cabot
Activated carbon sorbents are tailored reactions in the raw material at tempera-
for specific applications mainly based on tures between 100 and 400°C.
pore size and pore volume requirements. Charring. Higher-molecular-weight or-
Porosity and other parameters are con- ganic materials are converted to a car-
trolled by the following: 1) raw material bonaceous char residue at temperatures
selection; 2) activation process condi- of 400–600°C. At this point, incipient
tions; and 3) post-processing steps. porosity and increased internal surface
Depending on the application, activated area begin to form. A B
carbon may be in the form of powder Activation. Activation is generally con-
(PAC), granule (GAC) or extrudate (EAC). ducted in a steam atmosphere at tem-
All three forms are available in a range of peratures between 700 and 1,050°C,
particle sizes. depending on the pore structure of the
carbon being produced. The desired re-
Raw materials action is shown in Equation (1).
Almost any carbon-containing mate-
rial can be used to produce activated C + H2O ➞ CO + H2 (1) C D
carbon. In practice, economics and FIGURE 2. This series of diagrams il-
target product properties are the deter- This reaction gasifies portions of the lustrates pore development during steam
activation
mining factors in the selection of raw solid carbon to create pore volume.
materials. The base raw material has a Typically, about half of the carbona-
significant impact on the final product ceous char material entering the activa-
properties, including pore size distribu- tion step will be reacted away to create
tion and volume, hardness and purity. the desired internal pore structure. The
Most commercial activated carbons diagrams in Figure 2 depict the develop-
are manufactured from the following ment of porosity during steam activation.
raw materials: Chemical activation is used to pro-
• Coal (anthracite, bituminous, sub- duce carbons with pore structures and
bituminous, lignite) compositions that are somewhat differ-
• Coconut shell ent from those in steam-activated car-
• Wood bons. For example, chemically activated
Some types of activated carbon are wood has higher mesoporosity and
produced from less conventional raw higher oxygen content than a steam-
materials, such as peat, olive stones, activated carbon. The chemical activa-
fruit pits, petroleum coke, pitch, syn- tion process consists of mixing raw bio-
thetic polymers, scrap tires and waste mass with a strong dehydrating agent
cellulose materials. and heating to about 400 to 700°C. The
Raw materials may undergo pre-pro- dehydrating agent (typically phosphoric
cessing steps to control size, form and acid or zinc chloride) extracts the mois-
other properties. They may be crushed, ture from the raw material and fixes the
milled, briquetted or mixed with binders volatile component of the biomass while
and extruded prior to activation. the activation occurs. The degree of
activation is determined by the ratio of
Activation processes raw material to dehydrating agent and
Activated carbons are manufactured via by the heating time and temperature.
one of two processes: steam activation After activation, the product is extracted
at high temperature or chemical activa- to yield a highly porous activated carbon
tion using a strong dehydrating agent. product and the the dehydrating agent
Steam activation is the most com- is recovered.
monly used method for activated car- Chemical activation with potassium
bon production. It is performed in rotary hydroxide is of great recent interest be-
kilns, shaft kilns, multi-hearth furnaces cause it can produce highly micropo-
or fluidized beds, and proceeds through rous carbons with specific surface areas
the following steps: at or beyond the theoretical value for
Drying. Activated carbon raw materi- graphene (about 2,600 m2/g).
als in commercial use contain residual
moisture that must be removed before Post-processing
activation can take place. Following activation, activated carbon
Devolatilization. Volatile organic com- sorbents may undergo a series of post-
pounds (VOCs) are formed by cracking processing steps, including the following:

CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM JULY 2017 33


Cabot

0.9 Bituminous
range of applications. Silver is commonly
0.8 Lignite
used to disinfect water. A more special-
Wood
ized example is impregnation with metal
0.7
Peat
salts and amines for military gasmasks.
Pore volume, mL/g

0.6 On a larger scale, impregnation is used


0.5 to promote the oxidation of mercury in
0.4 coal-fired utility fluegas applications.
0.3 Products for enhanced sulfur removal
0.2
are impregnated with potassium iodide
or sodium hydroxide. Another example
0.1
of impregnation by end-users is the de-
0 position of precious metals on activated
< 2 nm 2-50 nm > 50 nm
Pore diameter carbon to form heterogeneous catalysts.
Re-activation. Some granular and ex-
FIGURE 3. The distribution of pore vol- Washing. Activated carbon may be truded products can be re-activated
umes differs depending on the starting acid-washed to reduce ash content and and recycled after use to minimize cost
material for the activated carbon
remove soluble impurities, such as iron. and environmental impact. In this pro-
Varying levels of increased purity are re- cess, spent carbon loaded with organic
quired for some applications, including contaminants is thermally treated in a
double-layer capacitors, pharmaceuti- process similar to steam activation. Re-
cals and food and beverages. activation desorbs and destroys volatile
Sizing. Granular products may be contaminants and restores much of the
sieved to specific particle size ranges. original pore volume and adsorptive ca-
Common mesh-size specifications pacity. Typical product loss during re-
range from 20 x 40 to 4 x 8 mesh (ap- activation is 5–15%, requiring makeup
proximately 0.4 mm x 0.8 mm to 2 mm with virgin material.
x 5 mm). Extrudates are produced with
diameters ranging from 0.8 to 5 mm and Adsorption fundamentals
length-to-diameter ratios between about Activated carbon sorbents remove low
1:1 to 4:1. Granule and extrudate sizes concentrations of chemicals (adsorbates)
are specified to balance mass transfer from a fluid (liquid or gas) by adsorption,
and pressure drop. Powder products the process of accumulation of materials
are often ground in roller, hammer or onto a solid surface. Adsorption occurs
jet mills to achieve a target particle-size within the activated carbon pore struc-
distribution (PSD), often specified by the ture by two distinct mechanisms: physi-
terms d5, d50 and d90, which are mea- cal and chemical adsorption.
sures of particle diameters. D50 (median Physical adsorption. Molecules are
particle size) can range from 5 to about attached to the carbon surface by van
20 micrometers (µm). Smaller particles der Waals attractive forces. These in-
improve mass transport, but can lead termolecular forces are very weak and
to filterability challenges. Tight control of diminish with increasing distance be-
PSD can optimize the balance. tween the carbon surface and the ad-
Shaping. Powdered activated car- sorbate molecule. Because the weak
bons may be formulated with binders attractive forces are greatly dependent
and shaped into cylinders, tubes, hon- on distance, physical adsorption occurs
eycombs and other extruded forms to primarily within pores that have a radius
optimize surface-to-volume ratio and only a few times greater than the molec-
pressure drop for various applications. ular diameter of the adsorbed molecule.
Granules and extrudates may also be Pores that are smaller than the size of
formed into filter blocks and plates using the impurity molecule are inaccessible
polymeric binders. and do not participate in the adsorp-
Impregnation. Some contaminants, tion process. Pores that are significantly
such as formaldehyde, elemental mer- larger than the adsorbate molecule are
cury and hydrogen sulfide are not ad- not as effective at adsorption because
sorbed on activated carbon. Chemical the attractive force diminishes as the
impregnation can add functionality to the distance between the pore surface and
carbon sorbent to catalyze a reaction or the adsorbate is increased.
promote chemisorption. Activated car- Adsorption occurs after the impurity
bon manufacturers add functionality for a molecule has diffused into the carbon
34 CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM JULY 2017
Landfill gas mixture Process & Industrial user
(methane w/C02) treatment
H2S removal
system Electricity
generation
Commercial user
Moisture
separator
Activated
Activated carbon
carbon

Landfill
well Boiler
room
Siloxane Processed gas
Landfill Blower removal
Additional
processing

Biogas system Residential user

Gas collection Gas control and processing Gas utilization

pore structure to an adsorption site. The tion isotherm. The Freundlich isotherm is FIGURE 4. This schematic diagram shows
process is diffusion-rate-limited and the commonly used to empirically define this the collection, purification and use of bio-
gas from a landfill site
large pores play a role in transporting relationship. The Freundlich adsorption
adsorbate to the adsorption sites. Phys- isotherm equation is shown here:
ical adsorption is an equilibrium process
and is very dependent on the concen- Ccarbon = kfCwater1/n (2)
tration of the adsorbate in the solution.
The relationship between the amount Where:
of adsorbate on the surface versus that in Ccarbon = concentration of adsorbate
the solution is described by the adsorp- adsorbed on carbon

Circle xx on p. 62 or go to adlinks.chemengonline.com/66430-xx Circle xx on p. 62 or go to adlinks.chemengonline.com/66430-xx

CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM JULY 2017 35


Coconut AC Lignite AC Factors affecting performance
Factors that affect the performance of
activated carbons can come from the
specifics of the application, or from the
100
activated carbon itself.
Application-related factors. Several
factors can aid or hinder adsorption.
AC capacity NOM/
AC capacity DI, %

75
The principal factor is the molecular size
50
of the compound being adsorbed. Ac-
tivated carbon adsorption increases as
the size of the molecule being adsorbed
25
increases. Certain types of functional
groups on the impurity molecule can
0 also affect its adsorbability.
0 5 10 15 Because the physical adsorption
PCB-118 conc. (ng/L)
process is an equilibrium reaction, the
FIGURE 5. This diagram shows a com- Cwater = equilibrium concentration of concentration of the molecule to be ad-
parison of lignite- and coconut-based ac- adsorbate in solution sorbed strongly affects the amount ad-
tivated carbon performance with 50 mg/L
natural organic material (NOM) Kf and n are constants for a given HOC sorbed, as described by the adsorption
and carbon at room temperature isotherm. The solubility of the adsorbed
The partition coefficient (Ccarbon / compound is also important, with lower
Cwater) can be calculated from Freun- solubility resulting in greater adsorption.
dlich equation at a given equilibrium Adsorption rate increases with tem-
concentration. If a single compound is perature. However, desorption rate also
being adsorbed by activated carbon, all increases with temperature and it is not
pores of a suitable size are available for possible to predict the net effect in liquid-
adsorption and the amount of material phase applications. The principal reason
adsorbed is the maximum achievable for adsorbing at elevated temperatures in
by the particular carbon. the liquid phase is to lower viscosity and
If several adsorbate molecules are increase diffusion rate. In gas-phase ap-
present, there can be competition for plications, adsorption always decreases
the adsorption sites. In that situation, with higher temperature.
the larger impurity molecules will block Activated-carbon-related factors. In
some of the smaller pores. This may re- adsorption applications, the most criti-
duce the carbon’s ability to adsorb the cal performance parameter is the distri-
smaller-sized adsorbates. bution of pore size and volume. Since
Chemical adsorption. Chemical ad- adsorption occurs almost exclusively in
sorption refers to the direct reaction of pores just a few times larger than the ad-
the adsorbed molecule with an active sorbate molecule, it is the pore volume
site on the carbon surface. As a result of within this size range that determines
the reaction, a chemical bond is formed adsorption capacity. The highly porous
between the adsorbate and the carbon nature of activated carbon gives rise to
surface. The active sites on the carbon surface areas as large as 3,000 m²/g.
surface involved in chemisorption are Pore sizes are classified as micro-,
mainly functional groups that contain meso- or macropores, according to the
oxygen and alter the electron balance conventions of the International Union
of the carbon surface. If the molecule of Pure and Applied Chemisty (IUPAC;
being adsorbed is chemically bound to iupac.org). Micropores with widths less
the carbon surface (shared electrons), than 2 nm are useful for adsorbing small
the process is termed chemisorption. molecules, especially in vapor applica-
If the adsorbed molecule resides only tions. Mesopores, ranging in width from
temporarily on the carbon surface, picks 2 to 50 nm, are in the right size range
up an electron, and then leaves the car- to adsorb many contaminant materi-
bon surface, the process is described as als. Macropores greater than 50 nm in
catalytic conversion. This is the mecha- width have minimal adsorption capac-
nism responsible for the dechlorination ity, but are critical in determining ad-
reaction used by bottlers to convert free sorption kinetics within the particle. The
chlorine in water to chlorides. larger pores provide transport paths for
molecules to diffuse into the mesopores
36 CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM JULY 2017
and micropores, where adsorption High purity is critical in some appli-
takes place. Figure 3 compares the cations. Food, beverage and potable
pore distribution of four different ac- water applications require low levels
tivated carbons from a variety of raw of extractables. Pharmaceutical acti-
materials and activation processes. vated carbons must have ultra-high
Surface area can be determined purity and full traceability. Emerging
by nitrogen adsorption using the uses in double-layer capacitors and
BET (Brunauer, Emmet, Teller) other electrochemical applications
method. Pore size distribution can depend on high purity for extended
be quantified by examining the ad- cycle life.
sorption and desorption of nitrogen,
carbon dioxide and other adsor- Application types
bates. Mercury porosimetry is well Activated carbon sorbents are used
suited to measure macropore and in two broad application classes:
large mesopore volume. However, vapor and liquid purification. Within
it is more common and convenient each class are examples of two
to measure and rank activated car- types of fluid-sorbent contacting.
bon performance using specific ad- These are PAC dosing and GAC/
sorbates that mimic the application. EAC packed columns. Beyond purifi-
Examples include iodine adsorption cation, activated carbons are used in
to assess small pore capacity and a number of specialized applications.
dye molecule adsorption (methylene In PAC dosing systems, activated
blue, bromophenol blue, and so on) carbon particles are injected into the
to assess medium-sized pores. In contaminated fluid, dispersed within
some cases, the characterization the fluid for an appropriate contact
test is directly related to the final ap- time, and then removed by sedimen-
plication, as in the case of molasses tation or filtration. PAC dosing may
decolorizing efficiency as a predictor be used in batch or continuous in-
of performance in sugar applica- jection systems. PAC contact times
tions, and butane working capacity range from 0.05 to 2 seconds in gas-
as a performance metric for carbons phase systems and 1 to 60 minutes
used to control automobile gasoline in liquid-phase batch applications. In
vapor emissions. municipal water treatment, PAC may
Particle size and distribution im- be added continuously as a slurry or
pact performance in both PAC and powder and then can be removed
GAC applications. For PAC, size and by flocculation, sedimentation and
size distribution correlate to mass- filtration. In coal-fired utility mercury
transfer resistance and filterability. removal, PAC is injected into the
In batch applications, a fine particle fluegas through a distribution lance
size provides rapid adsorption, but and removed in the electrostatic pre-
also a high pressure drop and slow cipitator or fabric filter.
filtration when removing the sorbent. In packed-bed systems, fluid flows
The best balance of performance is through a static bed of GAC or EAC.
often found by narrowing the size As the contaminant concentration
distribution. In GAC and extrudate in the fluid decreases, the loading
packed-bed applications, size is on the carbon increases, creating
again related to mass-transfer resis- a concentration gradient along the
tance and pressure drop. column. The mass-transfer zone is
Durability is of particular concern defined by the gradient between
for GAC and EAC forms. Particles the inlet concentration existing in
must be able to resist damage and the fully loaded bed and the outlet
fines formation during transport, col- concentration. Breakthrough occurs
umn loading and use — especially if when the mass-transfer zone travels
the application involves column back- to the exit of the column. Packed-
washing. Activated carbons for gold bed systems are sized based on
extraction have some of the most either calculated or experimentally
stringent durability requirements. Du- determined isotherms, contact time
rable particles are also required to based on estimated or measured ki-
minimize losses during re-activation. netics and mass transfer, and pres-
Circle xx on p. 62 or go to adlinks.chemengonline.com/66430-xx

CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM JULY 2017 37


sure drop requirements. bic digestion using animal manure or
Vapor-phase purification applications vegetation. The main constituents of
cover a wide range of contaminant mol- biogas are methane and carbon diox-
ecules from mercury to volatile organic ide, however, it also contains undesir-
materials. Some specific examples in- able impurities like hydrogen sulfide
clude gasoline vapor in automobile evap- (H2S), siloxanes and VOCs. These un-
orative-loss-control devices, mercury wanted impurities are present in low
in coal-fired utility fluegas and dioxin in concentrations, but must be removed
incinerator offgas. Another vapor-phase to reduce combustion equipment dam-
application is pressure- or temperature- age and downtime, to ensure emission
swing adsorption for solvent recovery targets are met, and to meet gas-purity
and hydrogen purification. Impregnated specifications. After purification, the
carbons are used in military gasmasks biogas can either be sent to an engine
and industrial respirators to protect per- to generate power, sold into the natu-
sonnel from toxic gases. An emerging ral gas grid or sold as a transportation
fuel in the form of biomethane. Figure 4
shows where activated carbon adsorp-
One of the most effective technologies for high- tion is used in a typical biogas system.
performance impurity removal in biogas is a two-step One of the most effective technolo-
gies for high-performance impurity re-
treatment with activated carbon moval in biogas is a two-step treatment
with activated carbon. For optimal per-
application in this area — removal of hy- formance, an operator will first direct a
drogen sulfide and siloxanes from biogas humid gas through an activated carbon
— is highlighted below. bed where H2S is reduced to elemental
Activated carbon sorbents are used sulfur by a catalytic process. After H2S
to purify a wide range of liquid systems, removal, the gas is dried and sent to a
including potable water, wastewater, in- separate activated carbon bed, where
dustrial process water, chemicals, phar- siloxane and VOC impurities are re-
maceuticals, foods and beverages. Re- moved by physical adsorption.
moval of taste and odor contaminants H2S purification. H2S is a hazardous
and harmful pollutants from potable chemical compound present in biogas.
water is one of the main purification ap- Biogas producers need to remove H2S
plications. Activated carbon is used to because it is poisonous, corrosive, flam-
remove precious metal catalysts after mable and malodorous. Traditionally,
synthesis of pharmaceutical active in- biological scrubbers, iron-oxide-based
gredients. Liquid sugar decolorization is media, or impregnated activated car-
one of the earliest activated carbon ap- bons have been used for H2S removal in
plications and remains important today. biogas. All technologies are capable of
Activated carbon is used to remove un- removing H2S; however, none of these
desirable taste compounds and color technologies has been optimized spe-
precursors from processed fruit juices. cifically for biogas. Biological scrubbers
Color removal from natural-gas liquids are very effective at removing high con-
is a more recent application. Activated centrations of H2S, but can be difficult to
carbon application in sediment remedia- operate and capital-intensive to install.
tion is covered in more detail below. Iron oxide media are low-priced, but
Non-purification applications of ac- generally demonstrate very low removal
tivated carbon include gold recovery efficiency. Iron oxide media are also no-
from cyanide leaching solutions, stor- torious for bricking (bridging between
age of gases, such as hydrogen and particles, forming lumps), which leads
methane, and electrodes for double- to costly and time-intensive removal ef-
layer capacitors and catalysts. forts. Chemically impregnated activated
carbon has a higher loading efficiency,
Biogas purification but can be quite expensive. Impreg-
Biogas is an environmentally friendly nated carbons can also pose safety
and sustainable fuel derived from the challenges, as they may cause bed fires
breakdown of organic matter. It is typi- due to an exothermic reaction with H2S.
cally produced at landfills, wastewater Many operators today are focusing on
treatment facilities, or through anaero- total cost of ownership and are choos-
38 CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM JULY 2017
ing a media or engineered solution that gas-limited source, they will likely prefer
offers the lowest cost per mass of H2S using activated carbon only. TSA units
removed. In making this calculation, the are also known to struggle with remov-
operator considers capital investment ing some lower-molecular-weight si-
for each technology, followed by analysis loxanes, which means that they often
of long-term operating costs. For media- require activated carbon polishing ves-
based solutions, they must consider the sels to remove all siloxane compounds.
amount of media needed to fill the ves- High concentrations of siloxane in a bio-
sel, the operating time until media satu- gas can lead to high operational costs
ration, the cost and time associated with to replace a standard activated carbon
media changeouts, and ultimately, how because much of the carbon pore vol-
the downtime impacts the ability to pro- ume is spent removing different families
cess gas. It is important to consider total of compounds from the gas. Specifi-
lifecycle cost in developing activated cally designed surface modifications to
carbons for biogas H2S removal. standard activated carbon can allow the
Siloxanes and VOC purification. Si- preferential adsorbtion of siloxanes over
loxanes are a group of synthetic com- VOCs. This results in significantly better
pounds used in the manufacture of per- siloxane loading capacity versus stan-
sonal hygiene, healthcare and industrial dard activated carbon products. Since
products. Disposal of these products this type of modified product does not
creates the risk of siloxane impuri- require a TSA unit to achieve high per-
ties in biogas, posing significant risks formance, it is a way that processors
depending on the final application. In could avoid the need to invest in an ex-
combustion engines, boilers, turbines pensive system upfront, but still realize
and fuel cells, siloxanes can form silica long-term savings.
that causes damage, destruction and Biogas is one of the more challenging
reduced operating efficiency. Siloxane gas-purification applications. Depend-
damage leads to higher operational ing on the source, the amount and the
costs and can seriously impact biogas speciation of impurities is constantly
upgrading and even prevent sales of variable. When deciding which adsorp-
contaminated biogas. tion technology to deploy, an operator
VOCs are impurities often found in bio- must consider many factors to deter-
gas derived from agriculture, landfills and mine the highest-performance and most
wastewater-treatment facilities. Depend- cost-effective solution for their site.
ing on the application, VOCs can be
viewed either as beneficial or detrimental Sediment remediation
to the quality of the gas. If the biogas is Sediments accumulated on the bot-
sent for combustion, the VOCs are often tom of waterbodies are sinks for toxic,
considered a beneficial high-Btu addi- bio-accumulative chemicals that can
tive. When biogas is further upgraded be transferred to invertebrates and fish
to biomethane, VOCs must be removed via food webs. Increasingly, remedia-
to prevent significant damage to mem- tion practitioners are turning to in-situ
branes and to limit emissions of sulfur treatment of contaminated sediments
oxides and nitrogen oxides. Pipeline gas to reduce the ecological and human-
has strict limits on VOC concentration. health risks posed by contaminants.
Activated carbon has traditionally This is mainly because conventional
been used for siloxane and VOC re- technologies (such as dredging and
moval, as it is effective at physically conventional sand capping) have not
removing both compounds. For dedi- always demonstrated risk reduction. A
cated siloxane removal, users often new approach of in-situ sediment treat-
opt for temperature-swing adsorption ment via contaminant sequestration in-
(TSA) using an activated-carbon bed volves placing activated carbon amend-
as a polishing step. The decision to use ments on contaminated sediments.
activated carbon versus TSA typically In this application, activated carbon is
comes down to operating conditions used to adsorb HOCs, such as poly-
and costs. TSA systems have relatively cyclic aromatic hydrocarbons (PAHs)
high upfront capital costs and also use and polychlorinated biphenyl (PCBs)
significant amounts of gas for regen- from sediment pore water. One chal-
eration. If an operator is pulling from a lenge in this application is interference

CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM JULY 2017 39


from natural organic matter (NOM). which can be calculated from a Freun-
Large organic molecules present in the dlich adsorption isotherm equation at a
water matrix, such as humic and fulvic given equilibrium concentration of the
acids, can cause blockage of the acti- contaminant in pore water.
vated carbon pore structure, leading to The author’s employer has generated
reduced adsorption capacity for target partition coefficients for a wide range
contaminants. Highly microporous car- of PAH and PCB contaminants for ac-
bons are particularly prone to blockage. tivated carbon products in this area.
Activated carbon with a tailored blend These data, combined with knowledge
of mesoporosity and microporosity is of site conditions, enables the design of
required for resistance to NOM and re- reactive caps using the CAPSIM model.
moval of target contaminants. Using the right activated carbon amend-
ment and cap design can provide in-situ
Increasingly, remediation practitioners are turning to sediment remediation solutions that pre-
vent breakthrough from contaminated
in-situ treatment of contaminated sediments to reduce sediments for 100 years or more.
human health and ecological risks
Summary remarks
Lignite-derived, activated carbon Activated carbon is a sorbent with wide-
grades now exist specifically for remov- ranging uses in the purification of vapor
ing PCBs, PAHs, dioxins and furans in and liquid systems, as well as special-
contaminated sediments. Activated ized uses in fuel storage, catalysis and
carbons developed for this application electrochemistry. Activated carbon can
have an optimal pore size distribution be tailored for specific applications by
that is designed to be highly effective for a combination of raw material selec-
the removal of these compounds in the tion, activation process conditions and
presence of NOM concentrations typi- post-processing, including shaping and
cal in sediment pore water. This broad chemical impregnation. Adsorption per-
pore-size distribution is critical for high formance is driven by pore size and vol-
performance, as NOM can partially or ume distribution, and other factors, such
completely block the adsorptive capac- as durability and particle size, influence
ity of more microporous carbons. Figure the choice of activated carbon for a spe-
5 compares microporous coconut AC cific application. Activated carbon can
and lignite AC with tailored porosity in be used in liquid or vapor applications
removal of PCB-118. The chart shows in either PAC or GAC/EAC form. Biogas
the ratio of PCB removal in water with purification and sediment remediation
50 mg/L NOM to removal in distilled are two recent applications that highlight
water and clearly demonstrates lignite’s the versatility of activated carbon sor-
resistance to pore blockage. bents for purification applications. n
Activated carbon amendments are Edited by Scott Jenkins
applied to the sediment either by direct
mixing, as a component in a geotextile Author
mat, or by incorporating it into a cap that Ken Koehlert is the product line and
creates a physical and adsorptive bar- technology director for Cabot Norit Acti-
vated Carbon (157 Concord Road, Bill-
rier between the contaminated sediment erica, MA 01821; Phone: 1-978-663-
and water. The cap consists of sand or 3455; Email: ken.koehlert@cabotcorp.
aggregate and carbon can be added as com). Koehlert has spent more than 30
years at Cabot, and has held positions
GAC or as a PAC coating applied to the in process and product R&D and manu-
surface of the aggregate. facturing across several of the compa-
ny’s businesses. He received B.S.Ch.E.
In order to design reactive caps using and M.S.Ch.E. degrees from the Massachussets Institute of
activated carbon, engineering firms Technology. Koehlert’s team develops and supports a wide
frequently use the CAPSIM model, de- range of products, including two unique activated carbons for
biogas purification. DARCO BG1 material optimizes the cost
veloped by professor Danny Reible of of H2S removed while limiting the concern for exothermic
Texas Tech University (Lubbock, Tex.; reactions associated with impregnated activated carbons.
www.ttu.edu). To assess and approve Cabot’s recently launched Norit Silpure product has a spe-
cifically de­signed surface to preferentially adsorb siloxanes
a specific activated carbon grade in a over VOCs. The team also works with Norit SedimentPure
reactive cap, engineering firms require activated carbons with tailored porosity to remove target con-
specific activated-carbon performance taminants in the presence of natural organic matter.
data, namely the partition coefficient,
40 CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM JULY 2017
Circle xx on p. 62 or go to adlinks.chemengonline.com/66430-xx