Improved Methods for Carbon
Adsorption Studies for Water and
Wastewater Treatment
Wei-chi Ying,a Wei Zhang,a Qi-gang Chang,a Wen-xin Jiang,a and Guang-hua Lib
a
East China University of Science and Technology, Shanghai 200237, China; wcying@ecust.edu.cn (for correspondence)
b
Shanghai Coking and Chemical Corporation, Shanghai 200241, China
Published online 25 January 2006 in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/ep.10122
An improved method was developed to rank acti-
vated carbon in removing organic water pollutants.
The simple and standardized evaluation method uses a
set of four adsorptive capacity indicators: phenol, io-
dine, methylene blue, and tannic acid numbers; those
four indicator compounds were selected because they
cover the molecular size range of most organic water
pollutants. An improved microcolumn rapid break-
through (MCRB) test method was developed from the
existing HPMC (high-pressure minicolumn) and RSSCT
(rapid small-scale column test) methods by simplifying
the experimental procedure and using readily avail-
able low-cost pump, sampler, piping, and fittings. This
method can be practiced in an ordinary environmen-
tal laboratory to select the best carbon, to verify the
treatment effectiveness, and to estimate the adsorption
treatment cost based on the observed capacity utiliza-
tion rate for carbon in the adsorber without the prob-
lems often encountered with using small and mini
traditional columns. The benefits of the four-parameter
carbon selection method and the MCRB method were
demonstrated by adsorption isotherm and break-
through data for several indicator compounds and
organic water pollutants. These improved methods will
enable efficient carbon adsorption studies necessary for
more applications of carbon adsorption technology in
water and wastewater treatment. © 2006 American Insti-
tute of Chemical Engineers Environ Prog, 25: 110 –120, 2006
Keywords: carbon selection, capacity indicators,
micro column, rapid breakthrough, MCRB, HPMC,
RSSCT
© 2006 American Institute of Chemical Engineers
110 July 2006
INTRODUCTION
Activated carbon, a powerful adsorbent, is very ef-
fective for removing a wide variety of organic pollut-
ants from aqueous influents. In the United States and
many other developed countries, activated carbon ad-
sorption technology is often selected for treatment of
water and wastewater influents to meet stringent efflu-
ent discharge limits. However, its application potential
is still undeveloped in China for three reasons: (1) the
concept of using either granular or powder activated
carbon is not generally known, (2) simple and effective
methods for carbon selection and adsorption studies
are not commonly available [1–3], and (3) no commer-
cial carbon regeneration service is available for remov-
ing the spent carbon and for supplying low-cost reac-
tivated carbon.
Before the best treatment process can be developed
for a large-scale water and wastewater treatment appli-
cation, a feasibility study is usually conducted first to
screen and to rank potentially applicable treatment
technologies such as carbon adsorption, oxidation,
precipitation, filtration, and biodegradation. A treatabil-
ity study is then conducted to confirm the effectiveness
of the preferred treatment technologies, to obtain im-
portant process design parameters for designing a full-
scale treatment system using the best technology, and
to estimate the treatment cost under realistic operating
conditions. For a potential carbon treatment applica-
tion, the feasibility study is a comprehensive laboratory
test program of adsorption isotherm experiments to
identify some commercial activated carbons with high
adsorptive capacities for select pollutants (target com-
pounds) to be removed from aqueous influents, and
the treatability study is a series of adsorption column
breakthrough experiments to select the best carbon, to
Environmental Progress (Vol.25, No.2)
Table 1. Carbon adsorption study parameters.

Parameter
Equilibrium adsorptive capacity
Organic loading of carbon in the
adsorber
Powdered carbon dose required in
a mixed reactor
Granular carbon exhaustion rate in
an adsorber
Formula
X/M (mg/g) ⫽ (C0 ⫺ Cf)V/carbon dose (g) C0 and Cf: initial and final
concentration (mg/L); V: sample volume (L)
Q (mg/g) ⫽ CinVf/total carbon in the adsorber (g) Cin: influent
concentration (mg/L), V: total volume treated (L), f: average
removal rate of the breakthrough experiment
PC (g/L) ⫽ (Cin ⫺ Ceff)/(X/M at Ceff) Cin and Ceff: influent and
effluent concentration (mg/L), X/M at Ceff: adsorptive capacity at
Ceff (mg/g)
GC (g/L) ⫽ Cin/(X/M at Cin) X/M at Cin: adsorptive capacity at Cin
(mg/g)

Table 2. Carbon requirement calculation.

How much carbon will be required to reduce the concentration of a pollutant from 100 to 1 mg/L,
given its Freundlich adsorption isotherm as: X/M (mg/g) ⫽ 13.0C f0.355
Powdered carbon dose
required in a mixed
reactor PC (g/L) ⫽ (Cin ⫺ Ceff)/(X/M at Ceff) ⫽ (100 ⫺ 1)/13.0 ⫻ 10.355 ⫽ 7.62 g/L
Granular carbon required in
an adsorber Gc (g/L) ⫽ Cin/(X/M at Cin) ⫽ 100/13.0 ⫻ 1000.355 ⫽ 1.50 g/L

verify the treatment effectiveness, and to estimate the
adsorption treatment cost based on the observed ca-
pacity utilization rate for carbon in the adsorber. With-
out simple and easy methods to select only a few high
potential carbons and to conduct the adsorption break-
through experiments, the necessary study will become
very time consuming and costly, making carbon ad-
sorption less attractive relative to other treatment alter-
natives.
There are indeed many published physical (specific
area, pore volume, particle size, hardness, ash content,
apparent density, pressure drop, and bed expansion vs.
flow) and adsorptive properties (iodine number, meth-
ylene blue number, carbon tetrachloride capacity) for
commercial activated carbons; however, they have not
been properly integrated to allow an easy and quick
screening of activated carbon for aqueous-phase appli-
cations. Although using a set of four well-defined ca-
pacity indicators (phenol value, iodine number, meth-
ylene blue number, and tannin value) for selection of
high potential carbon was fairly successful and that
those indicators were found to be well correlated to
pore size distribution (PSD) of the carbon particles [1,
3, 4], the method has not been widely practiced pri-
marily because it uses two ranking schemes (value and
number) that might have been confusing to some read-
ers.
Methods for conducting the necessary adsorption
breakthrough experiments are well known. Depending
on the nature of the pollutants (volatility, adsorbability,
biodegradability, and concentration in the feed), sam-
ple availability, type, and scale of the study (on-site or
off-site, bench or pilot study), the most effective break-
through experiments may use small and mini size tra-
ditional or pressurized micro carbon columns [1, 2,
5–7]. Although carbon columns of different sizes have
all been used with varying degrees of success, there is
yet no report of how to conduct the most cost effective
breakthrough experiments for a specific application.
Although some rapid column test methods have been
used for many years in the United States [8 –10], the
costly test equipment (pump, auto sampler) and the
lack of clear descriptions of system construction, test
conditions (particle size, flow rate, pressure), data anal-
ysis, and interpretation have certainly discouraged
many rightful applications of this important technique.
The objectives of this report are : (1) to present the
fundamental concept of carbon adsorption technology
for water and wastewater treatment, (2) to define a set
of simple and easily obtainable indicators of adsorptive
capacity to screen high potential activated carbons for
aqueous-phase adsorption, (3) to create a simple data-
base of the capacity indicators for popular commercial
carbons that can be used to identify which are effective
for removing water pollutants, (4) to develop a simple
and low-cost MCRB test procedure that can be prac-
ticed in an ordinary environmental laboratory to select
the best carbon and to estimate the capacity utilization
for carbon in the adsorber, and (5) to show how the
improved methods for carbon selection and column
breakthrough experiments can result in an efficient
adsorption study for a specific application.
FUNDAMENTALS OF CARBON ADSORPTION TREATMENT TECHNOLOGY
Activated carbon is used for aqueous-phase adsorp-
tion applications either as powder activated carbon in
mixed reactors or as granular activated carbon in ad-
sorbers. The fundamentals and applicability of the two
carbon adsorption technologies are quite different. A
certain dose (g/L) of powdered carbon is introduced to

Environmental Progress (Vol.25, No.2) July 2006 111


Figure 1. Carbon adsorption treatment process and
capacity utilization rate.
a mixed reactor to achieve desired concentration re-
ductions for select pollutants (target compounds),
whereas granular carbon in well-designed adsorbers
can remove them to meet very stringent discharge lim-
its for these compounds.
For all potential applications of adsorption technol-
ogy, a series of carbon isotherm experiments are first
conducted for some candidate carbons in the feasibility
study stage; the resulting adsorptive capacities and the
final residual (equilibrium) concentrations are corre-
lated by the Freundlich adsorption isotherm model to
allow selection of a few high potential carbons to be
evaluated in the treatability study stage in a series of
adsorption breakthrough experiments to select the best
carbon, to verify the treatment effectiveness, and to
estimate the adsorption treatment cost based on the
observed capacity utilization rate for carbon in the
adsorber under actual treatment conditions. Table 1
presents calculation methods for the important adsorp-
tion study parameters and Table 2 presents the esti-
mated powdered and granular activated carbons re-
quired for treating a wastewater. It is clear that granular
carbon treatment technology is more efficient in an
application that requires a very high degree of target
compound removal. Indeed, the granular carbon treat-
ment process has been successfully used in meeting ef-
fluent discharge limits of ⬍1 part per billion
(ppb) [5, 7].
Figure 1 presents relationships of capacity utilization
rates of different breakthrough curves and the carbon
bed change criteria. For situations requiring a high
degree of target compound removal and/or displaying
early breakthrough (Curves C and D), two large ad-
sorbers in series mode of operation is often the best
treatment process, given that carbon in the leading
adsorber may be heavily loaded to achieve a high
utilization rate (at a higher C1 than would be possible
using only one adsorber), whereas the acceptable ef-
fluent quality (C2) is ensured by the polishing treatment
of the second adsorber [1, 7]. These are the important
112 July 2006
concepts for application of carbon adsorption technol-
ogy in water and wastewater treatment.
EXPERIMENTAL
A large number of adsorption isotherm and column
breakthrough experiments were performed on several
indicator compounds and common water pollutants
using a wide variety of popular activated carbons, re-
sulting in an improved method for carbon selection and
an improved method for the breakthrough experi-
ments. To keep this report at a reasonable size, only the
most important results and summary are presented
here; the detailed experimental procedure and result
discussions are presented in two related articles [11,
12]. The major equipment, instruments, and chemicals
used in this study are summarized in Table 3.
Carbon Adsorption Isotherm Experiments
Phenol, iodine, methylene blue, and tannic acid
were selected as the indicator compounds because
they cover the molecular size range of most organic
water pollutants that can be effectively removed by
carbon adsorption [1, 3]. Methyl-tert-butyl ether
(MTBE), 2,4-dichlorophenol, and a red dye X3B were
used to verify the relative adsorptive capacities pre-
dicted by the four capacity indicators of candidate car-
bons. Standard procedures, with improvements such as
smaller-size samples, were used for the iodine and
methylene blue runs [1, 4, 7, 8, 13, 14]. All isotherm
experiments used a head-to-bottom rotation method
[5], to provide effective mixing for the carbon particles
(⬍180 mesh) and the test solutions; the time required
to establish the equilibrium condition was determined
for each adsorbate, such as 2 h for phenol, 8 h for
methylene blue, and 12 h for tannic acid. The test
results, adsorptive capacity (X/M) and final residual
(equilibrium) concentration (Cf), were correlated by
the Freundlich adsorption isotherm and plotted with
the data for easy comparison of relative capacities.
Adsorption Breakthrough Experiments
Adsorption breakthrough experiments were per-
formed using three sets of carbon columns (Figure 2):
small, mini, and micro columns. Our micro column
method—the micro column rapid breakthrough
(MCRB) method—was developed from improvements
and simplification of Calgon’s high-pressure minicol-
umn (HPMC) method [9] and the rapid small-scale col-
umn test (RSSCT) method [10, 15, 16] commonly used
in the United States to allow its practice in an ordinary
environmental laboratory. The fundamentals of the
MCRB technique, experimental apparatus, detailed test
procedures, results, and discussions are covered else-
where [12]. Uncrushed and unsieved carbon particles
were used in the small and mini traditional columns
operating at empty bed contact times (EBCTs) similar
to the full-size carbon adsorbers (⬎10 min), whereas
much smaller carbon particles (120 –180 mesh) and a
shorter EBCTs (⬍30 s) were used in the MCRB runs.
Two series of breakthrough experiments were con-
ducted in mini carbon columns in the upflow mode of
operation (see Figures 9 and 10 below), and other
Environmental Progress (Vol.25, No.2)
Table 3. Equipment, instruments, and chemicals.

Item Model and grade Manufacturer/vendor

Particle area/porosity analyzer ASAP 2020M Micromeritics (USA)
GC 7890 II Shanghai Techcomp Co.
UV/VIS spectrophotometer UV2000 Unico Shanghai Instrument
Auto sampler Modified BSZ-160* Shanghai Huxi Analytical Instrument
Tubing metering pump HL-2 Shanghai Huxi Analytical Instrument
Piston metering pump ES-B10 IWAK1 Pumps Co. (Shanghai)
Coffee grinder 4041/KSM2 Braun Co. (USA)
Phenol AR Shanghai Feida Co.
Iodine AR Shanghai Lingfeng Chemical Reagent
Methylene blue CP Sinopharm Chemical Reagent
Tannic acid AR Shanghai Sanpu Chemicals
MTBE Industrial Shanghai Refinery
2,4-Dichlorophenol CP Sinopharm Chemical Reagent
X3B Industrial Huachang Polymer Co. (Shanghai)

*Modified to provide additional flow channel and overflow discharge.

Figure 3. Adsorption isotherms for phenol.

Figure 2. Apparatus for breakthrough experiments.

Left to right: micro (5, 5, 8 mm ID), mini (15, 15
mm), small (36, 36 mm) carbon columns; bottom:
piston pumps, tubing pump, auto sampler.

breakthrough experiments were conducted in small

and mini size traditional columns in the downflow
mode of operation with the effluent line raised above
the top of the carbon section to minimize shortcircuit-
ing and/or uneven flow rate in the adsorber (see Fig-
ures 10 –12 below).

RESULTS AND DISCUSSION

Carbon Adsorptive Capacity Indicators

Experimental results of adsorption capacities for
phenol and tannic acid on five brands of activated
carbons are presented as the Freundlich isotherms in Figure 4. Adsorption isotherms for tannic acid.
Figures 3 and 4. These isotherms allow easy compari-

Environmental Progress (Vol.25, No.2) July 2006 113

Table 4. Definition and application of carbon adsorptive capacity indicators.

Indicator Definition Application Note

Phenol number The amount (mg) of phenol adsorbed by Capacity for small 180/phenol value*
1 g of carbon in a solution having an compounds
equilibrium phenol concentration of
20 mg/L.
Iodine number The amount (mg) of iodine adsorbed by Total surface area; Initial concentration ⫽
1 g of carbon in a solution having an capacity for small– 0.1 N (12.691 g I2/L)
equilibrium iodine concentration of medium
0.02 N. compounds
Methylene blue The amount (mg) of methylene blue Capacity for medium Initial concentration ⫽
number adsorbed by 1 g of carbon in a compounds 20,000 mg/L
solution having an equilibrium
methylene blue concentration of 1
mg/L.
Tannic acid The amount (mg) of tannic acid Capacity for large 18,000/tannin value**
number adsorbed by 1 g of carbon in a compounds
solution having an equilibrium tannic
acid concentration of 2 mg/L.

*Phenol value: The carbon dose (g/L) required to reduce phenol concentration from 200 to 20 mg/L [1, 4].
**Tannin value: The carbon dose (mg/L) required to reduce tannic acid concentration from 20 to 2 mg/L [1, 4].

Table 5. Experimental procedure and data for phenol number.

Carbon type: Shanghai 18 Test sample volume: 40 ml, initial pH ⫽ 6.5

Buffer solution: A. dissolve 26 g Na2HPO4 in 250 mL of water, adjust pH to 6.5 using phosphoric acid; B: 1/40
of Buffer A.
Stock solution: 200 mg/L phenol solution prepared by Buffer B.
Carbon slurry: 10 mg/mL prepared by Buffer B.
Procedure:
1. Add a total of 10 ml of the carbon slurry and Buffer B to each sample bottle containing 30 mL of the phenol
stock solution.
2. Mix the bottle content for a period long enough to establish the equilibrium condition.
3. Filter the sample and measure the light absorption (absorbance at 268 nm). Dilute the sample if abs ⬎ 1.0.
4. Find the residual concentration based on a standard curve (5–100 mg/L); calculated the corrected residual
concentration (Cf) using the sample with no carbon as the initial concentration (C0).
5. Correlate the adsorption capacity (X/M) and Cf by the Freundlich adsorption isotherm.

Carbon/slurry/Buffer B Light absorption Residual Corrected residual X/M*

(mg/mL/mL) abs (dilution) conc. (mg/L) conc. (mg/L) (mg/g)
0/0.0/10 0.452 (5) 152.9 150.0
5/0.5/9.5 0.389 (5) 131.3 128.8 169.5
10/1.0/9.0 0.348 (5) 117.2 115.0 139.9
20/2.0/8.0 0.271 (5) 90.83 89.11 121.8
40/4.0/6.0 0.741 50.40 49.44 100.6
60/6.0/4.0 0.374 25.23 24.75 83.50
80/8.0/2.0 0.184 12.20 11.97 69.02
100/10.0/0.0 0.102 6.576 6.452 57.42
Freundlich adsorption isotherm: X/M ⫽ kC 1/nf
k ⫽ 30.103, 1/n ⫽ 0.3274, correlation coefficient ⫽ 0.9822
Phenol number (X/M at Cf ⫽ 20 mg/L) ⫽ 80.3 mg/g

*X/M (mg/g) ⫽ (C0 ⫺ Cf, mg/L) ⫻ volume (L)/carbon dose (g).

sons of the carbon’s capacity and thus provide a simple and methylene blue numbers, were selected to replace
method for carbon selection. Phenol number and tan- the phenol and tannin values as indicators of activated
nic acid number, defined in the same manner as iodine carbon’s adsorptive capacities for organic adsorbates.

114 July 2006 Environmental Progress (Vol.25, No.2)

Table 6. Experimental procedure and data for iodine number.

Carbon type: Taixi 12⫻40 Test sample volume: 88 mL

Stock solution: 0.1 N (19.052 g KI and 12.691 g I2/L); saved in a dark bottle.
Procedure:
1. Add a quantity of pulverized carbon to each test bottle, add 8 mL of 5% HCl, mix well and heat over an
electric heater to boil for 60 s. Add 80 mL of the stock solution and shake vigorously for 2 min or longer to
establish the equilibrium conditions.
2. Filter to remove the carbon particles. Measure the light absorption (absorbance at 600 nm)
3. Find the iodine concentration* based on a standard curve (0.005–0.04 N); calculated X/M.

Light absorption Residual X/M Correction I2 no.

Carbon (g) abs (dilution) conc. (N) (mg/g) factor** I2 no. (average)
0.755 0.474 0.0224 1013 0.983 995 994
0.804 0.416 0.0197 989 1.004 993

*Use 0.4% HCl to prepare standard solutions and for dilution of the filtered test samples.
**Estimated from the published table [7].

Table 7. Experimental procedure and data for methylene blue number.

Carbon type: Taixi ZJ-15B Test sample volume: 35 mL

Stock solution: 20,000 mg/L methylene blue solution; saved in a dark bottle.
Procedure:
1. Add the prescribed amount of pulverized carbon in each of labeled 125-mL Erlenmeyer flask.
2. Add 35 mL of the stock solution; mix for a period long enough to establish the equilibrium condition; filter
and measure the light absorption (absorbance at 613 nm). Dilute the sample if abs ⬎ 1.0.
3. Find the residual concentration based on a standard curve (2–10 mg/L), calculate X/M.
4. Estimate the methylene blue number from the Freundlich isotherm curve for the data.

Carbon dose Light absorption Residual conc. X/M Methylene blue

(mg) abs (dilution) (mg/L) (mg/g) numbera
2.207 0.212 (1000) 2243 281.6 —
2.600 0.207 (50) 109.8 267.8 232
3.006 0.195 2.086 232.8 230

Freundlich adsorption isotherm: X/M ⫽ kC f1/n

k ⫽ 230.24, 1/n ⫽ 0.0276, correlation coefficient ⫽ 0.9826
Methylene blue number (X/M at Cf ⫽ 1 mg/L) ⫽ 230 mg/g

*For samples with a residual concentration within 0.4 –500 mg/L, the methylene blue number can be estimated from
the published table [7].

Table 4 presents the definition, application, and con-
version formulas for the four capacity indicators. Table
5 presents the experimental procedure and data for
calculation of phenol number; a similar table can be
used for isotherm runs for tannic acid (for calculation of
tannic acid number), other organic compounds of in-
terest, or gross organic concentration parameters such
as total organic carbon (TOC), chemical oxygen de-
mand (COD), and light absorbance at a specific wave-
length [1, 4, 5, 11]. A carbon slurry was used to intro-
duce very small amounts of carbon; otherwise,
pulverized carbon may be added directly to the test
sample.
Tables 6 and 7 present the experimental procedures
and data for calculation of iodine number and methyl-
ene blue number, respectively, showing methods for
estimating the two indicators using multiple samples.
Table 8 presents the four capacity indicators for
many popular activated carbons. Based on the good
correlations of those indicators with the carbon’s PSD
[1, 3, 17], the three bituminous coal– based Xinhua
carbons would have good capacities for small to me-
dium size adsorbates, whereas its ZJ-15 would have far
less capacity for large adsorbates than PJ8x30 and PJ-
09. Shanghai 18, Shanghai coconut shell, Taixi ZJ-15A
and ZJ-15B, and Huahui A would all have good capac-
ities for small adsorbates but were not competitive in
removing medium to large pollutants. On the other
hand, Shanghai fruit shell, Taixi 8x30, and Huahui B
would have good capacities for adsorbates of all sizes.
Relative to the sample obtained 2 years ago, the new
Taixi 8x30 II had higher iodine and methylene blue
numbers but lower phenol and tannic acid numbers.
The Stockroom carbon was the least effective for re-

Environmental Progress (Vol.25, No.2) July 2006 115

Table 8. Adsorptive capacity indicators for popular activated carbons.*

Methylene Tannic acid

Activated carbon Phenol no. Iodine no. blue no. no.
Calgon F-300 107 1020 300 36.7
Calgon Service, reactivated 86.5 823 238 39.8
Cecarbon 30 97.3 1004 274 28.7
Cecarbon 830DC 79.6 1120 365 176
Polifos Actibon, wood 26.6 939 348 55.2
Norit HD-3000, lignite 54.7 554 116 86.1
Shanghai fruit shell 113 1012 292 113
Shanghai coconut shell 109 1202 327 16.4
Shanghai 18, cylinder 81.9 910 225 7.73
Taixi ZJ-15A, cylinder 64.0 843 208 12.3
Taixi ZJ-15B, cylinder 64.8 939 230 7.93
Taixi 8x30 90.1 738 192 60.3
Taixi 8x30 II 74.6 902 204 8.10
Taixi 12x40 65.1 991 299 13.0
Huahui A 71.9 906 204 12.5
Huahui B 74.8 887 272 95.8
Xinhua PJ 8x30 77.6 1017 254 50.9
Xinhua ZJ-15, cylinder 78.5 903 242 10.9
Xinhua PJ-09 82.1 1012 255 39.5
Stockroom, cylinder 61.9 543 ⬍150 33.3

All are bituminous coal– based granular carbons, except as noted.

Figure 5. Pore diameter distribution: (a) cumulative pore volume; (b) cumulative surface area.

moving small to medium size adsorbates of all carbons
studied; the low cost of this carbon suggests that its
pore structure was not fully developed because of
incomplete activation. Calgon F-300 and Cecarbon 30
would have similar adsorptive properties as those of
the Chinese bituminous coal– based activated carbons.
As further evidences of the strong dependency of car-
bon’s PSD on the raw material, the lignite-based carbon
ICI HD-3000 and the wood-based Polifos Actibon
would have better capacities for large adsorbates. The
Calgon Service carbon’s higher tannic acid number
suggested that many of the spent Calgon F-300’s fine
pores were enlarged during the high-temperature reac-
tivation conditions.
Verification of Surface Area/Pore Volume Predictions
To demonstrate that the four-parameter carbon eval-
uation method is capable of predicting the relative
surface area and pore volume for competing carbons,
the Brunauer–Emmett–Teller (BET) surface area and
porosity measurements were performed on five acti-
vated carbon samples. The total surface areas for Stock-
room, Taixi 8x30, Huahui A, Shanghai fruit, and Shang-
hai coconut carbons were, respectively, 660, 782, 870,
974, and 1090 m2/g, in the same order as their iodine
numbers (543, 609, 775, 1012, and 1202); therefore, the
iodine number is an excellent indicator for activated
carbon’s total surface area.

116 July 2006 Environmental Progress (Vol.25, No.2)

Figure 6. Adsorption isotherms for MTBE.

Figure 7. Adsorption isotherms for 2,4-

dichlorophenol.
From the PSD curves shown in Figures 5a (cumula-
tive pore volume) and 5b (for cumulative surface area),
Taxi 8x30 was the first to show micro pores in the
smallest pore size fractions (3–10 Å in diameter); how-
ever, in the slightly larger pore size fractions, its cumu-
lative pore volume and surface area were soon over-
taken by Shanghai fruit, Shanghai coconut, and
Stockroom samples, whereas Huahui A continued to
have the least of both. Except for the Stockroom carbon
in which the pore structure was not fully developed,
such results were consistent with the order of their
phenol numbers. In the medium pore size fraction of
10 to 20 Å, the order of surface area for the five carbons
(Figure 5b) were the same as their iodine number and
methylene blue number (Table 8). Whereas large pores
(⬎20 Å) were absent in Shanghai coconut and Huahui
A, they continued to be present in the other three
carbon samples; their tannic acid numbers could also
predict this information. The BET measurements thus
verified the utility of these four carbon capacity indica-
tors (phenol, iodine, methylene blue, and tannic acid Figure 8. Adsorption isotherms for X3B.
numbers) in predicting the relative surface area and
pore volume for most activated carbons.

Verification of Capacity Predictions for Typical Water
Pollutants
MTBE and phenol have nearly the same molecular
weight and aqueous-phase molecular size [18]. Figure 6
shows the capacities of five carbons for MTBE were in
the same order as for phenol; therefore, the phenol
number is an excellent indicator for a carbon’s capacity
for this type of small adsorbates. 2,4-Dichlorophenol
has a molecular weight (163) between phenol (94) and
iodine (254); Figure 7 shows the carbons’ relative ca-
pacity for the compound was well predicted by their
iodine numbers and phenol numbers. The red dye
X3B’s molecular weight is fairly large (615), between
methylene blue (320) and tannic acid (1701); thus two
carbons with high capacities for tannic acid and two
carbons with high capacities for methylene blue were
selected for the verification runs. Figure 8 shows they
all had respectable capacities for X3B; the relatively
lower capacity exhibited by the coconut shell carbon
could be explained by its lack of large pores (⬎20 Å,
Figure 5b). Therefore, the four capacity indicators may
be used for selection of a few high potential activated
carbons to be fully evaluated in an efficient carbon
adsorption study for a potential water and wastewater
treatment application.
Mini Column Breakthrough Experiments: Iodine and
Methylene Blue
Two adsorption breakthrough runs for iodine were
performed using mini columns operating in the upflow
mode (5 g carbon, flow rate: 0.54 mL/min, influent
concentration: 10,000 mg/L). Figure 9 results showed
that iodine was removed in an ideal manner (nearly
100% use of the adsorptive capacity in both columns
consistent with the iodine number order), suggesting
that one large carbon adsorber would be sufficient for
removing pollutant of this type. The results (Figure 10)
of two series of breakthrough experiments for methyl-
ene blue (EBCT: 20 min, influent concentration: 2000
mg/L): upflow runs of Calgon Service and Cecarbon

Environmental Progress (Vol.25, No.2) July 2006 117

Figure 9. Mini column breakthrough curves for
iodine (5 g carbon; flow: 0.54 mL/min; C0: 10,000
mg/L).
Figure 10. Mini column breakthrough curves for
methylene blue (EBCT: 20 min; C0: 2000 mg/L).
830DC (5 g carbon each) and downflow runs of Taixi
8x30 (10 g) and Taixi 12x40 (7.8 g) have shown that
order of methylene blue breakthrough was predicted
by their methylene blue numbers; the calculated capac-
ity utilization rates (Calgon Service: 59%; Taixi 8x30:
83%; Cecarbon 830DC: 85%; and Taixi 12x40: 91%)
were in the same order as their capacities, that is, a
greater utilization rate was observed in the carbon with
a higher capacity. The close fit of the two series of
experiments has demonstrated that studies conducted
at different times, locations, and operating conditions
can in fact be compared when their performances are
plotted against the number of bed volumes treated.
New Micro Column Rapid Breakthrough Method:
Phenol
Adsorption breakthrough experiments for phenol
were performed in small (117 g carbon, 10 min EBCT)
and mini (11 g, 10 min) traditional as well as micro
(1.05 g, 7 s) columns, and the results, as shown in
Figure 11, showed that nearly all of the carbon’s capac-
ity for phenol was used in the column treatment. The
test results have therefore validated the MCRB as an
effective method for conducting breakthrough experi-
ments in a small fraction (1–5%) of time required by the
118 July 2006
Figure 11. Phenol breakthrough curves (carbon: Taixi
8x30 II; C0: 100 mg/L).
Figure 12. MCRB system pressure vs. flow rate
(column ID: 5 mm; carbon: Taixi 8x30 II).
traditional methods and that potable water could be
used to replace deionized water for preparation of the
feed solution because the two MCRB curves were
nearly identical. The two MCRB curves were smooth
while the breakthrough curves for the two larger col-
umns fluctuated near the end of the runs as a result of
the uneven flow rate. The MCRB treatment perfor-
mance was unaffected without the use of a flow equal-
izer and the system pressure was ⬍50 psig (Figure 12),
well within the range of a common piston pump. The
readily available low-cost pump, sampler, and other
necessary items allowed the practice of this simplified
MCRB method in an ordinary environmental laboratory
to select the best carbon, to verify the treatment effec-
tiveness, and to estimate the adsorption treatment cost
based on the observed capacity utilization rate for car-
bon in the adsorber.
Verification of the MCRB as a Carbon Selection
Method: MTBE
The four MCRB breakthrough curves in Figure 13
(1.0 g carbon, 10-s EBCT) showed that the order of
MTBE breakthrough and the total MTBE removals were
in the same order of increasing phenol numbers of the
four activated carbons used in the study. The capacity
utilization for Taixi 12x40, Huahui A, Shanghai 18, and
Environmental Progress (Vol.25, No.2)

Figure 13. MCRB curves for MTBE (carbon: 1.0 g;
EBCT: 10 s; C0: 120 mg/L).
Taixi 8x30 were 60, 76, 91, and 96%, respectively,
consistent with the observation of higher capacity uti-
lization in the carbon of greater capacity. The results
have thus demonstrated the effectiveness of the MCRB
as an ideal carbon selection method in lieu of valid
adsorption isotherm data that are difficult to obtain,
such as those shown in Figure 6 for MTBE.
CONCLUSIONS
1. When carbon adsorption is the preferred technology
for treating an aqueous influent to meet stringent
discharge limits, two adsorbers in series mode of
operation often constitute the most cost effective
treatment process. The lead adsorber allows a high
utilization of carbon’s adsorptive capacity, whereas
the polish adsorber ensures excellent treatment per-
formance.
2. A simple and standardized four-parameter carbon
selection method (based on four indicators of car-
bon adsorptive capacity: phenol, iodine, methylene
blue, and tannic acid numbers) was developed to
screen high potential activated carbon for removing
organic compounds from aqueous solutions. The
four indicator compounds were selected because
they cover the molecular size range of most organic
pollutants to be removed by carbon adsorption.
3. A table of the four capacity indicators for all popular
commercial activated carbons is a useful database
for initial carbon selection to identify a few candi-
date carbons to be evaluated in a treatability study.
The database should be updated to reflect major
changes in carbon’s properties and/or when impor-
tant new carbons become available.
4. The existing micro column rapid breakthrough
methods (such as HPMC and RSSCT) were improved
with the use of less-costly test equipment and sim-
plified procedure to complete the breakthrough ex-
periment in a small fraction (1–5%) of time required
by using small or mini traditional carbon columns.
The validity and the benefits of this improved MCRB
test method were demonstrated by the results of
many isotherm and breakthrough experiments for
several indicator compounds and typical water pol-
lutants.
Environmental Progress (Vol.25, No.2)
5. The new MCRB method can be practiced in an
ordinary environmental laboratory. Depending on
the nature of the pollutants, sample availability, and
type and scale of the study, the most effective break-
through experiments may use small (⬎100 g), mini
(⬎5 g), or traditional or pressurized micro (⬍2 g)
carbon columns to select the best carbon, to verify
the treatment effectiveness, and to estimate the ad-
sorption treatment cost based on the observed ca-
pacity utilization rate for carbon in the adsorber.
6. These improved methods will enable efficient car-
bon adsorption studies necessary for more applica-
tions of carbon adsorption technology in water and
wastewater treatment.
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