Environ. Sci. Technol.
2000, 34, 686-692
Analysis of the Relationship
between H2S Removal Capacity and
Surface Properties of
Unimpregnated Activated Carbons
FOAD ADIB, ANDREY BAGREEV, AND
TERESA J. BANDOSZ*
Department of Chemistry and the Center for Water Resources
and Environmental Research, of the City College of New York,
New York, New York 10031
The H2S breakthrough capacity was measured on two
series of activated carbons of a coconut shell and a bituminous
coal origins. To broaden the spectrum of surface features
the samples were oxidized using nitric acid or ammonium
persulfate under conditions chosen to preserve their pore
structures. Then the carbons were characterized using
Boehm titration, potentiometric titration, thermal analysis,
temperature programmed desorption, sorption of nitrogen,
and sorption of water. It was found that the choice of
unimpregnated carbon for application as H2S adsorbent
should be made based on parameters of its acidity such as
number of acidic groups, pH of surface, amount of
surface groups oxygen, or weight loss associated to
decomposition of surface oxygen species. The results
obtained from the analyses of six unimpregnated carbon
samples suggest that there are certain threshold values of
these quantities which, when exceeded, have a dramatic
effect on the H2S breakthrough capacity.
Introduction
Problems associated with removal of odor from air have
become controversial issues, especially in urban areas. One
of the leading malodorants arising from sewage treatment
facilities is hydrogen sulfide (1). Activated carbons used for
removal of H2S from sewage treatment plants are generally
impregnated with caustic materials such as NaOH or KOH
or are otherwise modified (2). Air currents around odor-
generating facilities are initially washed in scrubbers, during
which they intake high levels of humidity, and are then blown
through activated carbon vessels. The residual H2S quickly
reacts with strong base and is immobilized. The presence of
humidity facilitates the reaction (3, 4). The carbon bed is
mostly used as a passive support for the caustic. Furthermore,
due to the energetic reactions of caustic materials, the
impregnation decreases the ignition temperature of the
carbon and poses a hazard of self-ignition.
The application of virgin (unimpregnated) activated
carbon for removal of H2S from air has been investigated
(5-12) ,and considerable removal capacities have been
reported for carbons at temperatures around 200 C. The
* Corresponding author e-mail: tbandosz@scisun.sci.ccny.cuny.
edu; telephone: (212)650-6017; fax: (212)650-6107.
Present address: The Graduate School of the City University of
New York, Department of Civil Engineering.
Present address: Institute for Sorption and Problems of Endo-
ecology, Kiev, Ukraine.
686 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 34, NO. 4, 2000
use of virgin activated carbon for H2S removal at the ambient
temperatures, although the subject of recent studies (3, 4,
13-16), is not common yet. The major difficulty seems to lie
with the fact that little is known with certainty about the
mechanism of reaction on the carbon surface. Unlike
caustics-impregnated carbons, the reactions on virgin car-
bons are very complex since they involve the broad spectrum
of physical and chemical properties of the adsorbent. Most
of the results reported so far have been based on an empirical
analysis of specific types of carbon, and sometimes they
appear to be contradictory (3-5, 9-12).
The objective of this research is to identify the surface
features of unimpregnated activated carbons of different
origins that are important for their performance as adsorbents
of hydrogen sulfide. Although many studies published so far
have explored the effect of dynamic conditions such as
concentration of H2S, content of air, and humidity, we
underline here the role of carbon surface. The search for
surface characteristics of unimpregnated carbons is driven
by disadvantages of caustics-impregnated carbons that have
been used so far as effective H2S adsorbents. These disad-
vantages are as follows: (i) low temperature of self-ignition,
(ii) low capacity for physical adsorption, (iii) special precau-
tions used with caustics, and (iv) high costs of adsorbents.
The advantage of caustics-impregnated carbons used as H2S
adsorbents is the fast kinetic of the oxidation reaction (2),
but they are efficient only till KOH or NaOH is not exhausted
(15). The oxidation occurs in the liquid phase where high pH
(around 10) provides high concentration of hydrogen sulfide
ions. The mechanism of H2S immobilization by the unim-
pregnated carbons significantly differs, but when the condi-
tions for completion are attained (low concentration of
hydrogen sulfide in air), the capacities of two categories of
carbons are comparable (13). To broaden the spectrum of
materials, the carbons were oxidized with nitric acid and
ammonium persulfate (17-19). On the basis of the results
obtained, the relationships between the observed H2S
breakthrough capacity and the major properties of carbons
are analyzed. We explore the general features that either
govern the behavior of carbons as H2S adsorbents and/or
are common for the two types of materials chosen for this
study. The carbons were oxidized since all commercial
carbons have some amount of oxygen-containing groups on
the surface. Those groups are known to significantly change
the catalytic activity and/or selectivity of carbons in various
oxidation reactions (20, 21). Moreover, storage of activated
carbon results in its oxidation, which affects the performance
as adsorbent and catalyst.
Experimental Section
Materials. Two activated carbons of different origins are
chosen for this study. The first sorbent, RB3, is a peat-based,
pellet-shaped carbon (pellet size: 2 1 mm), manufactured
by Norit Americas Inc. The second, S208c, supplied by
Waterlink Barnebey Sutcliffe, is a granular activated carbon
(irregular granules of about 5 1 mm) obtained from coconut
shell. Each carbon was washed in a Soxhlet apparatus to a
constant pH of the leachate to remove the water-soluble
impurities and then dried in oven at 120 C. These initial
samples are referred to as N0 (Norit) and S0 (Waterlink
Barnebey Sutcliffe).
The initial samples were oxidized with 15 M nitric acid
with a ratio of 5 mL of acid/g of carbon at room temperature.
Then the carbons were washed, dried, and designated as N1
and S1. Two other oxidized samples were prepared using a
saturated solution of ammonium persulfate as an oxidant in
10.1021/es990341g CCC: $19.00 2000 American Chemical Society
Published on Web 01/12/2000
1 M sulfuric acid at a ratio of 10 mL/g of carbon at room
temperature. These samples are referred to as N2 and S2.
Methods. H2S Breakthrough Capacity. Moist air (relative
humidity 80% at 25 C) containing 0.3% (3000 ppm) H2S was
passed through a column of either palletized or granular
carbon (length 370 mm, diameter 9 mm) at 0.5 L/min at
room temperature. The column was widened at the top 60
mm to a diameter of 23 mm to minimize the wall effect. The
H2S emission was monitored by an Interscan LD-17 H2S
continuous monitor system (electrochemical detector) in-
terfaced with a computer data acquisition program. The test
was stopped at a breakthrough concentration of 500 ppm.
The breakthrough capacity of carbon was then calculated
using the integrated area above the breakthrough curve
(difference between inlet 3000 ppm and breakthrough
concentration curves), the mass of carbon, and the flow rate.
Boehm Titration. The oxygenated surface groups were
determined according to the method of Boehm (22). One
gram of carbon sample was placed in 50 mL of the following
0.05 N solutions: sodium hydroxide, sodium carbonate,
sodium bicarbonate, and hydrochloric acid. The vials were
sealed and shaken for 24 h, then 5 mL of each filtrate was
pipetted, and the excess of base or acid was titrated with HCl
or NaOH. The numbers of acidic sites of various types were
calculated under the assumption that NaOH neutralizes
carboxyl, phenolic, and lactonic groups; Na2CO3 neutralizes
carboxyl and lactonic groups; and NaHCO3 neutralizes only
carboxyl groups. The number of surface basic sites was FIGURE 1. H2S breakthrough results for N (A) and S (B) series of
calculated from the amount of hydrochloric acid that reacted samples.
with the carbon.
Potentiometric Titration. Potentiometric titration mea- Sorption of Nitrogen. Nitrogen isotherms were measured
surements were performed with a DMS Titrino 716 automatic using an ASAP 2010 (Micromeritics) at -196 C. Before the
titrator (Metrohm). The instrument was set at the mode when experiment, the samples were heated at 120 C and then
the equilibrium pH was collected. Subsamples of the carbons outgassed at this temperature under a vacuum of 10-5 Torr
of about 0.100 g in 50 mL of 0.01 M NaNO3 were placed in to constant pressure. The isotherms were used to calculate
a container maintained at 25 C and equilibrated overnight the specific surface area, SN2; micropore volume, Vmic; volume
with the electrolyte solution. To eliminate the influence of of mesopores, Vmes; and total pore volume, Vt. All of the above
atmospheric CO2, the suspension was continuously saturated parameters were calculated using Density Functional Theory
with N2. The carbon suspension was stirred throughout the (DFT) (23, 24).
measurements. Volumetric standard NaOH (0.1 M) was used Sorption of Water. Water sorption experiments were
as titrant. The experiments were done in the pH range of carried out at 20 C using Micromeritics ASAP 2010 with a
3-10. Each sample was titrated with base after acidifying the vapor sorption kit. The instrument was equipped with a
carbon suspension. homemade thermostated system controlled by a Fisher
pH of Carbon Surface. The sample of 0.4 g of dry carbon Scientific Isotemp Refrigerated Circulator. Samples were first
powder was added to 20 mL of water, and the suspension heated at 120 C and outgassed to 10-5 Torr. HPLC-grade
was stirred overnight to reach equilibrium. Then the sample water used as an adsorbate was free of any dissolved gases.
was filtered, and the pH of the solution was measured. Using ASAP 2010, water uptake is able to be measured starting
Thermal Analysis. Thermal analysis was carried out using from very low relative pressure (p/po 10-3) (4, 19, 25). Each
TA Instruments thermal analyzer. The instrument settings point of the isotherm is recorded after equilibrium is reached.
were as follows: heating rate, 10 deg/min; and either air or The isotherms were measured to relative pressure about 0.3.
nitrogen atmosphere with 50 mL/min flow rate.
Temperature-Programmed Desorption. Temperature- Results and Discussion
programmed desorption (TPD) was conducted on a Pulse The breakthrough performance of initial and oxidized
ChemiSorb 2705 (Micromeritics) using helium as a carrier carbons is summarized in Figure 1. The breakthrough
gas. The dried carbon samples of about 0.2 g were placed in capacities measured for N0, N1, N2, S0, S1, and S2 are 95.8
a U-shaped quartz reactor and heated at 120 C for 3 h under ( 5.11, 47.7 ( 0.64, 28.2 ( 1.83, 111.8 ( 4.5, 14.5 ( 2.3, and
a helium flow (40 mL/min). Then the flow was changed to 11.5 ( 1.4 mg of H2S/g of carbon, respectively. However, the
18 mL/min, and after the baseline was stabilized, the time periods for initial carbons after which 500 ppm is reached
temperature was raised to 1000 C at a rate of 10 deg/min. are similar, so the shape of the breakthrough curves shows
The decomposition products of surface oxygen-containing slightly better performance in the case of S0 material.
groups (CO, CO2, and H2O) were measured by a thermo- Oxidation with nitric acid and ammonium persulfate sig-
conductivity detector. Three series of experiments were nificantly decreases the capacity, especially for S series of
carried out for each carbon sample in order to distinguish carbons. In both cases, ammonium persulfate oxidation
the products of desorption. In the first step, the combined caused the most dramatic decrease in the performance. This
amount of CO, CO2, and H2O was determined. In the second decrease was expected due to a decrease in pH as a result
step, the TPD curve for CO was measured using a cold trap of the introduction of more acidic groups. It supports the
with liquid nitrogen located before the detector. Then the proposed pathways of H2S oxidation on unimpregnated
curve representing CO and CO2 was recorded using a cold wood-based carbons presented elsewhere, where the pH of
trap with dry ice. The instrument was calibrated by injection surface was pointed out as an important factor (16). To link
of precise volumes of the pure gases (CO and CO2). the measured capacity of unimpregnated carbons to their

VOL. 34, NO. 4, 2000 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 687

TABLE 1. pH and Numbers of Functional Groups from Boehm
Titration (mequiv/g)
sample pH carboxylic lactonic phenolic basic
N0 7.72 0.00 0.12 0.00 1.00
N1 4.47 0.31 0.41 0.32 0.45
N2 3.59 0.56 0.81 0.33 0.49
S0 6.89 0.17 0.02 0.12 0.51
S1 4.58 0.29 0.32 0.35 0.26
S2 3.66 0.65 0.42 0.65 0.12
surface features, the detailed analysis of carbons was carried
out with the stress on features important for the sorption
process such as surface chemistry and structural parameters.
To check the extent of oxidation process, Boehm titration
was performed (22). The used bases enable us to identify the
number of carboxyls, lactones, and phenols. The results
obtained along with the pH values of carbon surface are
collected in Table 1. Comparison of the initial materials shows
that the S0 sample is more heterogeneous than N0. In the
case of N0 carbon, only lactonic groups represent strong acids.
The samples also differ in the amount of basic species; the
N0 sample has twice the basic groups as the S0.
Oxidation with nitric acid significantly increases the
number of acidic groups, decreases the number of basic
groups for both carbons, and creates carboxylic acids in the
case of N1 material. The decrease in the number of basic
species as compared to the initial samples is likely due to the
conversion of insoluble components of inorganic matter such
as carbonates into soluble nitrates. On the other hand,
oxidation with ammonium persulfate is more effective for
S2 than for N2. The S2 sample shows a significant increase
in the number of carboxylic and phenolic groups along with
a 75% decrease in the number of basic species.
More details about the strength of acidic and basic groups
present on the surface of our carbons are derived from
potentiometric titration experiments. The method of analysis,
assumptions, and numerical approach used (SAIEUS) are
described elsewhere (17, 18, 26). The distributions of acidity
constants for species on the surface of carbons are shown
in Figure 2. As proposed elsewhere, the species having pKa
smaller than 8 are assigned to strong carboxylic acids, and
those with pKa greater than 8 are assigned to phenols (18).
The results obtained for initial carbons indicate the existence
of a larger number of strong acids in the case of S0 as
compared to N0, which is in agreement with the results of
Boehm titration. However, the surface groups seem to be
more heterogeneous in the case of the N0 sample where more
peaks are revealed (at pKa about 4.2, 5.6, 6.8, and 7.5).
After oxidation with nitric acid, a slightly larger number
of groups is detected for N1 carbon with disappearance of
the peak at pKa of about 6.8 present for the initial material
(Figure 2A). This peak is likely related to the presence of
inorganic matter, which was removed from the carbon during
acid treatment. The changes in the acidity after oxidation
are more pronounced in the S series, as shown from the
Boehm titration results. The S1 sample shows a significant
increase in the population of groups with pKa smaller than
5.5 (Figure 2B), along with the creation of new strongly acidic
species, beyond the limits of our experimental window (17).
After oxidation with ammonium persulfate, even though
peaks at similar positions are revealed for both carbons, the
number of groups is larger in the case of S2 material. Those
results indicate similarity in the quality of groups created
using the same oxidant (18).
The results obtained from acid/base titration are in general
agreement with the pH values collected in Table 1. They
represent the average acidity of the carbon surface indicating
that S0 is more acidic than N0, but after oxidation only small
differences in pH remain between both carbons.
688 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 34, NO. 4, 2000
FIGURE 2. Acidity constant distributions for N (A) and S (B) series
of carbons.
The presence of oxygen groups on the surface of carbons
is also detected by means of TPD. The obtained TPD curves
are collected in Figure 3. The most acidic groups (carboxyls,
lactones) are desorbed as CO2 in the temperature range of
200-650 C, while less acidic (phenols, carbonyls) and basic
groups (pyrones) are desorbed mainly as CO or CO + CO2
at the temperature range between 500 and 1000 C (27, 28).
The amounts of volatile products formed during TPD
experiments are collected in Table 3. As expected, the total
amounts of CO and CO2 desorbed from oxidized carbons
significantly increases as a result of oxidation (27). The
presence of water is a result of the decomposition of
carboxylic groups. The TPD data confirm the results of
titrations and clearly show that oxidation with ammonium
persulfate creates more oxygen groups on the carbon surface
than does oxidation with nitric acid. The peak at 730 C
representing CO2 on the TPD curve for the N0 sample is likely
related to the presence of carbonate impurities. The titration
results showed that these species disappear after oxidation.
Another method providing fast and meaningful informa-
tion about surface chemistry is thermogravimetric analysis
(TG). The TG curves along with the weight derivatives (DTG)
obtained for both series of samples from the experiments
performed in nitrogen appear in Figure 4. Although tests are
carried out starting from room temperature, curves are
plotted from 120 C to take away the adsorbed water
interference. The data are corrected accordingly so that the
weight at 120 C is considered as 100%. The weight losses for
our carbons in the temperature ranges related to the presence
of strong and weak acids (28, 29) are reported in Table 2. For
the initial carbon, N0, the total weight loss is around 5% with
a significant peak between 500 and 800 C (Figure 3). This
peak likely represents the decomposition of the basic species
and/or inorganic matter that significantly contribute to the
chemistry of this material (highest ash content). After
oxidation, the total weight loss for both N1 and N2 carbons
is similar, but small differences exist at the low temperature
range where strong acids are expected to decompose (28).
Although similar behavior is observed for the S series, no
significant weight loss in the temperature range of 500-800
 TABLE 3. Weight Loss in Different Temperature Ranges and
Ash Content (%)
sample 120-500 C 500-800 C 120-1000 C ash content
N0 1.36 2.61 5.70 3.40
N1 4.05 4.08 10.73 3.01
N2 3.55 3.77 9.60 1.71
S0 0.59 1.60 4.21 0.00
S1 4.95 8.70 17.85 0.00
S2 5.58 6.64 16.26 0.00

FIGURE 3. Thermodesorption spectra.

TABLE 2. Amounts of Gases Thermodesorbed at Different

Temperature Ranges (mmol/g)
120-500 C 500-1000 C
sample CO CO2 H2O CO CO2 H2O total
N0 0.03 0.06 0.14 0.55 0.22 0.05 1.05
N1 0.10 0.45 0.16 1.68 0.40 0.01 2.80
N2 0.06 0.73 0.17 2.79 0.54 0.00 4.29
S0 0.08 0.35 0.14 2.08 0.31 0.02 2.98
S1 0.09 0.54 0.10 2.58 0.53 0.01 3.85
S2 0.11 0.99 0.27 4.22 0.49 0.00 6.08

C is found for the initial sample, S0 (Figure 4, Table 3). This
suggests that unlike N0, S0 is low in basic species and/or
inorganic matter (practically zero ash).
In the process of hydrogen sulfide adsorption on activated
carbons, structural parameters should play an important role
(4, 5, 14). They are calculated from nitrogen isotherms
FIGURE 4. Thermal analysis results for TG (A and C) and DTG (B
and D).
measured at -196 C using density functional theory (DFT)
(23, 24). The specific surface area, volume of micropores
(Vmic), volume of mesopores (Vmes), and total pore volume

VOL. 34, NO. 4, 2000 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 689

TABLE 4. Structural Parameters Calculated from Nitrogen
Adsorption (DFT)
sample SN2 (m2/g) Vmic (cm3/g) Vmes (cm3/g) Vt (cm3/g)
N0 790 0.31 0.06 0.47
N1 790 0.31 0.08 0.50
N2 800 0.33 0.05 0.49
S0 1030 0.39 0.02 0.52
S1 970 0.37 0.03 0.50
S2 880 0.32 0.04 0.46

FIGURE 6. Water adsorption isotherms at 20 C.

that the sorption capacity of S0 carbon is much higher than

FIGURE 5. Pore size distributions for the N (A) and S (B) carbon
series.
(Vt) are collected in Table 4. The initial carbons differ in
surface areas and pore volumes; the porous structure of the
S material is more developed than the N. Comparison of the
data indicates that in the case of N carbon oxidation does
not affect the pore structure, while for the S series a small
decrease in the surface area and micropore volume is noted
along with a slight increase in the volume of mesopores.
Detailed changes in the pore structure of the S carbons are
seen in the pore size distributions presented in Figure 5. It
is interesting to note that while oxidation with nitric acid
decreased the volume of pores smaller than 10 (a peak
centered at around 7 ), oxidation with ammonium persulfate
left these pores almost intact with a significant decrease in
the volume of pores represented by peak at about 15 .
The results reported in the literature indicate that in most
cases the presence of moisture enhances the adsorption and
oxidation of hydrogen sulfide (3, 4, 13). According to the
mechanism proposed by Hedden et al., dissociative adsorp-
tion of hydrogen sulfide has a significant impact on its
oxidation (10). A similar conclusion was reported in our
previous study (16). It is well-known that the affinity of
activated carbon to retain water depends on the number of
oxygenated groups present on the surface (19, 25, 30), which
are considered as primary adsorption centers. Further
adsorption of water on the already adsorbed water molecules
leads to the condensation in small pores even at relatively
low humidity. To investigate the affinity of our carbons to
retain moisture, water adsorption isotherms were measured
at relative pressure smaller than 0.3 at 20 C. Figure 6 shows
N0. This result is expected since the S carbon has more
oxygenated groups and more developed microporosity (25,
26). After oxidation with nitric acid, water uptake significantly
increases for the N1 carbon, while for the S1 only a small
enhancement is observed. This difference follows the effect
of oxidation described above. After oxidation with ammonium
persulfate, the amounts adsorbed for N2 and S2 are almost
the same due to similar surface chemistry and structural
parameters (Table 1, Table 4).
To identify the surface parameters crucial for the en-
hancement of the hydrogen sulfide adsorption capacity, the
dependence of the measured capacity on the surface features
described above was analyzed. No direct relationship between
the performance of carbons as H2S adsorbents and the
parameters of pore structure was found; however, higher
micropore volume along with smaller pores result in en-
hanced capacity (Figure 1, Figure 5, and Table 4). As we
indicated elsewhere for wood-based carbons (16), im-
mobilization of hydrogen sulfide within pore structure is a
result of its dissociation in the preadsorbed water film to
HS- ion and adsorption of the latter followed by its oxidation.
The extent of dissociation depends on the local pH in the
pore system, which is governed by surface chemistry. Taking
into account these findings, the dependence of breakthrough
capacity on six quantities affecting dissociation of hydrogen
sulfide in the pore structure has been analyzed based on the
performance of the six samples studied. These are pH of
carbon surface, number of basic groups, total number of
acidic groups, water adsorption at 30% relative humidity,
weight loss between 500 and 800 C [associated with the
destruction of weak acids such as phenols and carbonyls
(20, 21)], and amount of surface groups oxygen (Figure 7).
In all cases, a good linear correlation was not found. Analysis
of the plots presented in Figure 7 suggests that there is a
certain threshold value in each of those parameters beyond
which significant changes in the capacity occur. An estimate
of the threshold values may be as follows: a surface pH of
more than 4.5, 0.5 basic groups/g of carbon, 0.85 mequiv of
acidic groups/g of carbon, around 3 mmol of adsorbed
water/g of the carbon material, around 3% of weight loss
between 500 and 800 C, and 2 mol/m2 of surface groups
oxygen. An increase in pH and the number of basic groups
beyond the reported values increase the capacity, whereas
an increase in the other four parameters (number of acidic
groups, weight loss, surface groups oxygen, and water
adsorption) significantly decreases the performance of
carbons as H2S adsorbents.

690 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 34, NO. 4, 2000

FIGURE 7. Dependence of H2S breakthrough capacity on: (A) pH of carbon surface, pH of carbon suspension (with dissolved H2S); (B)
number of basic groups; (C) number of acidic groups; (D) water uptake at p/po ) 0.3 and 20 C; (E) weight loss at 500-800 C; (F) amount
of surface groups oxygen.

To explore the existence of a threshold in the pH value
of the carbon surface at our experimental conditions,
simplified calculations were performed based on the mech-
anism of H2S oxidation at low temperature (<100 C) and
humid conditions proposed in the literature (10-12, 31). It
involves (i) H2S adsorption on the carbon surface, (ii) its
dissolution in water film, (iii) dissociation of H2S in adsorbed
state in water film, and (iv) surface reaction with oxygen:
KH
H2Sgas 98 H2Sads
KS
H2Sads 98 H2Sads-liq
Ka
H2Sads-liq 98 HS-ads + H+
KR
2HS-ads + O*ads 98 2Sads + H2O
If the surface reaction (eq 4) is the rate-limiting step of
the H2S oxidation process (31), the degree of H2S dissociation
should be high enough to start its oxidation on the surface
(HS-ads H2Sgas). Combining eq 1 to eq 3, the following
expression can be derived to calculate the equilibrium HS-ads
concentration:
log (HS-ads) ) log (KS) + log (KH) + log (Ka) + pH +
log (H2Sgas) (5)
(1)
where log (Ka) ) -7.2 (32). Solubility of pure H2S at 25 C in
water is equal to 0.125 mol/L (32), which corresponds to KS
(2) ) 3.1. Adsorption constant, KH depends on the interaction
of H2S with carbon and should be determined independently
as a ratio of H2Sads to H2Sads-liq. For our evaluation, we assumed
(3)
that H2Sads is not higher than the solubility of pure H2S in
water. For 3000 ppm of H2S in the gas phase, it follows that
(4) KH ) 330. Substitution of KS, KH, and Ka values in eq 5 gives

where H2Sgas, H2Sads-liq, and H2Sads are concentrations of H2S
in gas, liquid, and adsorbed phases, respectively; KH, KS, Ka,
and KR are equilibrium constants for related processes
(adsorption, gas solubility, dissociation, and surface reaction
constants); O*ads is dissociatively adsorbed oxygen; and Sads
is the concentration of surface compounds as end products
of the surface oxidation reaction.
log (HS-ads) ) -4.2 + pH + log (H2Sgas) (6)
This simplified expression suggests that, for all carbons with
average surface pH >4.2, concentration of HS- in the
adsorbed state will be equal to H2S in a gas phase (100%
adsorption + dissociation), which is required for effective
H2S removal. The dependence of the ratio of concentration

VOL. 34, NO. 4, 2000 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 691

of HS- in the adsorbed state to the concentration of H2S in
a gas phase (HS-ads/H2Sgas) on the pH of carbon suspension
in water (with dissolved H2S) calculated using eq 6 is plotted
in Figure 7A. The estimated value of pH is lower than the first
dissociation constant (pKa) of H2S. This supports our
hypothesis presented elsewhere that a pH value only high
enough for mild dissociation of H2S is sufficient for its effective
removal (16). In such a situation physically adsorbed H2S,
upon dissociation in the water film to hydrogen sulfide ion
(HS-), becomes vulnerable to attack by oxygen and can be
oxidized to elemental S and sulfur oxides (8, 16). As seen
from Figure 7A, both calculated and experimental results
show the same trend expressed by a sharp increase of
adsorption capacity in the range of pH between 4 and 5.
Although calculated above threshold pH is equal to 4.2, the
threshold estimated from the data presented in Figure 7A
seems to be higher than 4.5. The discrepancy with the
calculated value of pH is due to the fact that pH >4.2 was
obtained from the simplified expression without the exact
value of the adsorption constant, KH. The calculation
presented above suggests the existence of the threshold;
however, it cannot be taken as an absolute value (N1 and S1
carbons have pH >4.2 but are not able to effectively remove
hydrogen sulfide). When the number of basic groups
increases, the capacity increases (Figure 7B) due to en-
hancement in the hydrogen sulfide dissociation. However,
the capacity increases only in accordance with the pore
volume of carbons (Table 4), which is the limiting factor for
the adsorption process.
When the number of acidic groups exceeds 0.85 mequiv/g
(Figure 7C), the surface becomes too acidic to promote the
dissociation of hydrogen sulfide, and only its physical
adsorption can occur (not high at room temperature). With
such a high number of groups, sorption of water is enhanced
even at low relative pressure (25, 26). Although tests carried
out under dry conditions have generally demonstrated
negligible capacities (13), it is seen from our experiments
that water uptake higher than the threshold value does not
increase the breakthrough capacities of unimpregnated
carbons (Figure 7D). In the case of carbons chosen for this
study, the affinity for water adsorption should not be greater
than 3 mmol/g to reach the maximum capacity. It is likely
that, when the affinity of carbons to adsorb water is very
high, the small pores are filled by condensed adsorbate (25,
26) and the direct contact of HS- with carbon surface in the
smallest pores is limited.
Another two parameters related to carbon acidity analyzed
in this study are the weight loss from TA experiments
associated with weak acids (Figure 7E) and the amount of
surface groups oxygen calculated from TPD (Figure 7F). As
in the cases presented above, threshold values can be noticed.
They are related to the acidity of surface and its effect on
dissociation of hydrogen sulfide.
Analysis of the results obtained for two series of carbons
(coconut shell and bituminous coal origins) as adsorbents
of hydrogen sulfide indicates that the choice of unimpreg-
nated activated carbons for application as H2S adsorbents
should be made based on surface parameters related to its
acidity. While at pH values above 5 considerable capacities
are observed, a more acidic environment, which decreases
the dissociation of H2S, quickly suppresses the process. The
consequent decrease in the concentration of HS- ions inhibits
H2S adsorption and its further oxidation. The capacity
significantly drops when the number of acidic groups exceeds
approximately 0.85 mequiv/g of carbon. Although some
humidity is crucial for effective removal of H2S, water effect
beyond this threshold value is secondary to the surface
chemistry of carbon. A reduced capacity is observed when
the affinity for water adsorption is too high and exceeds about
3 mmol/g of carbon. This is due to the filling of small pores
692 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 34, NO. 4, 2000
and its negative effect on the contact of dissociated HS- ions
with the carbon surface in micropores.
Although we realize that the number of data analyzed in
this paper is too small to formulate the well-defined new
carbon specification for industrial applications, the indication
of the existence of the threshold in surface acidity has been
demonstrated. This would suggest that, if unimpregnated
carbons are to be used as hydrogen sulfide adsorbents, their
long storage after the manufacturing process is not recom-
mended due to air oxidation of the carbon surface and a
decrease in the surface pH.
Acknowledgments
This research was supported by The New York City Depart-
ment of Environmental Protection. The authors thank
Professor Amos Turk for encouragement and discussions.
The help of Ms. Anna Kleyman in performing experiments
is appreciated. T.J.B. wishes to thank Dr. Jacek Jagiello for
providing SAIEUS program.
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Received for review March 25, 1999. Revised manuscript
received August 27, 1999. Accepted December 1, 1999.
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