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Activated carbon treatment of municipal solid waste incineration flue gas

Shengyong Lu, Ya Ji, Alfons Buekens, Zengyi Ma, Xiaodong Li and Jianhua Yan
Waste Manag Res published online 23 November 2012
DOI: 10.1177/0734242X12462282

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462282
2012
WMR0010.1177/0734242X12462282Waste Management & ResearchLu et al.

Original Article

Waste Management & Research

Activated carbon treatment of municipal

0(0) 1­–9
© The Author(s) 2012
Reprints and permission:
solid waste incineration flue gas sagepub.co.uk/journalsPermissions.nav
DOI: 10.1177/0734242X12462282
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Shengyong Lu, Ya Ji, Alfons Buekens, Zengyi Ma, Xiaodong Li and

Jianhua Yan

Abstract
Activated carbon injection is widely used to control dioxins and mercury emissions. Surprisingly little attention has been paid
to its modelling. This paper proposes an expansion of the classical Everaerts–Baeyens model, introducing the expression of
fraction of free adsorption sites, fs, and asserting the significant contribution of fly ash to dioxins removal. Moreover, the model
monitors dioxins partitioning between vapour and particulate phase, as well as removal efficiency for each congener separately.
The effects of the principal parameters affecting adsorption are analysed according to a semi-analytical, semi-empirical model.
These parameters include temperature, contact time during entrained-flow, characteristics (grain-size, pore structure, specific
surface area) and dosage of activated carbon, lignite cokes or mineral adsorbent, fly ash characteristics and concentration, and
type of incinerator plant.

Keywords
Activated carbon, adsorption, dioxins, Everaert–Baeyens model, lignite cokes, municipal solid waste incineration,
removal efficiency

Introduction
Municipal solid waste incineration is a source of dioxins, which
needs to be reduced effectively (Stockholm Convention).
Activated carbon injection (ACI) coupled with baghouse filtra-
tion (BF) is widely used as end-of-pipe treatment and was pro-
posed (European Commission, 2006) as best available technology
(B.A.T.). However, ACI is still applied empirically, leading to
potential wastage of activated carbon (AC) (Yang et al., 1999).
Therefore, this study established a model that predicts dioxins
removal efficiency and examines all salient factors affecting
adsorption in ACI + BF systems allowing the treatment process
to be controlled and optimized.
Activated carbon has a porous structure, tailored by its original
matrix (e.g. wood, peat, lignite, coal) and activation procedures.
Ideally, channels are wide at the surface to promote internal trans-
port and diffusion and become smaller inside the AC, constituting
an extensive micropore surface. Adsorbates of large molecular
size, however, cannot enter micropores (< 2 nm) and are thus
screened out. Yet, stronger adsorption occurs when pore size and
adsorbate molecular size are closer (Zhang, 1989). Optimal
adsorption occurs for ratios of pore diameter to adsorbate molecu-
lar diameter of only 1.7–3; however, this optimal ratio increases to
3–6 when AC is to be reused (Gu, 1999). Dioxin molecular sizes
are typically: (2,3,7,8-TCDD) long axis 1.37 nm, short axis 0.735
nm, thickness 0.35 nm; (2,3,7,8-TCDF) long axis 1.31 nm, short
axis 0.74 nm, thickness 0.35 nm (Nagano et al., 2000). OCDD and
OCDF are not much larger. Consequently, optimal adsorption of
dioxins requires an AC pore diameter of 2.3 to 4.1 nm (Xie, 2003).
The surface area of mesopores + macropores (2~20 nm) deter-
mines the adsorption capacity for dioxins: each gram of AC
adsorbs 105~115 ng dioxins or 10~25 ng dioxins per m2 surface
area of AC (Chi et al., 2006b). AC adsorption does not alter the
congener fingerprint of dioxins significantly (Chang and Lin,
2001; Everaert et al., 2003; Mori et al., 2005).
Dioxins in flue gas are distributed over both gas and particu-
late phase (G/P). Flue gas temperature, dust concentration and
characteristics (surface area, pore size, particle size, and chemi-
cal composition) all affect this partitioning (Mätzing et al., 2001;
Yan et al., 2006). The precise configuration of the air pollution
control device (APCD) is important. In some municipal solid
waste incineration plants dioxins in the G/P phase were measured
(Table 1) at the inlet of the APCD (Chi and Chang, 2005; Chi
et al., 2006a, 2006b).
Gas/particulate partitioning of dioxins is strongly affected by
dust filtration (Chi and Chang, 2005). Cyclones remove relatively
State Key Laboratory of Clean Energy Utilization, Institute for
Thermal Power Engineering, Zhejiang University, Hangzhou,
China
Corresponding author:
Zengyi Ma, State Key Laboratory of Clean Energy Utilization, Institute
for Thermal Power Engineering, Zhejiang University, 310027
Hangzhou, China
Email: mazy@zju.edu.cn, lushy@zju.edu.cn

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2 Waste Management & Research 0(0)

Table 1.  Fraction of vapour phase dioxins at the inlet of an ACI + BF systema.

APCD Sampling at Fraction of vapour Reference

the inlet of phase dioxins (%)
SDA (ACI) + BF SDA 42 Chi and Chang (2005)
CY + DSI (ACI) + BF DSI 58 Chi et al. (2006b)
CY + DSI (ACI) + BF DSI 72 Chi and Chang, (2005)
CY + DSI (ACI) + BF DSI 75 Chi et al. (2006a)
VS + WESP + FACB FACB 80 Chi et al. (2006b)
aACI,
activated carbon injection; BF, baghouse filter; CY, cyclone; DSI, dry sorbent injection; FACB, fixed activated carbon bed; SDA, spray dryer
absorber; VS, venturi scrubber; WESP, wet electrostatic precipitator.

Figure 1.  Typical flue gas cleaning options and scope of the model proposed. ACI, activated carbon injection; BF, baghouse
filter; CY, cyclone; DSI, dry sorbent injection; ESP, electrostatic precipitator; SDA, spray dryer absorber.

coarse dust (> 10 µm) only. Electrostatic precipitators (ESPs)
lower residual dust to typically 30–150 mg Nm−3. Modern three-
field ESPs reduce dust loads down to well below 10 mg Nm−3.
BFs show highest efficiency, with dust collection down to 0–3 mg
Nm−3. BFs thus eliminate almost all dioxins attached to particu-
late (on fly ash and neutralizing agents). Residual, vapour phase
dioxins can only be removed by adsorption (or catalytic oxida-
tion). Therefore, the efficiency of dioxins adsorption, ηg, further
refers to the vapour phase dioxins only.
Dioxins are adsorbed from flue gas in four types of gas/solids
contactors: (1) fixed-bed; (2) moving-bed; (3) entrained flow
adsorbers; and (4) wet scrubbers. Entrained flow units require
minimal investment and space. This article models their adsorp-
tion efficiency, using both empirical and fundamental parameters
that can be adapted to a particular plant. Then, salient inlet and
operating factors are analysed based on this model.
Adsorption model
Entrained flow adsorption
Powdered activated carbon is injected into the flue gas, together
with lime or hydrated lime slurry neutralizing acid gases. The
AC, fly ash, and lime flow and mix together with flue gas,
adsorbing dioxins and other semi-volatiles [such as polycyclic
aromatic hydrocarbons (PAHs)] in amounts proportional to their
concentration and adsorptivity. Adsorption is especially obvious
over the first metres of flow in common.
Filter cake adsorption
Finally, the flue gas enters into the baghouse filter and ideally is
evenly distributed over all bags. Particulate accumulates onto the
surface of the bags, by retaining particles of activated carbon, fly
ash, and lime, in amounts determined by their relative concentra-
tion. At that moment, their adsorption potential is not exhausted
yet: the cake further adsorbs dioxins from flue gas until the bags
are cleaned. The oval-shaped area in Figure 1 shows schematically
the principle of filter cake adsorption. Similar processes apply
when different neutralizing agents such as NaHCO3 are used.
Figure 1 presents the incinerator furnace and boiler, and pos-
sible pre-separation of fly ash. Black circles mark the battery lim-
its of the model developed in the present study. Typical dust loads
vary considerably, depending on each dust pre-separation option;
e.g. for a stoker incinerator:
•• Dust load after the boiler: 2 to 4 g Nm−3.
•• Dust load after boiler + cyclone: 0.4 to 1 g Nm−3.
•• Dust load after boiler + ESP: 30 to 150 mg Nm−3.
The adsorptivity on the neutralizing agents and dust are pertinent
factors. Typical orders of magnitude were estimated, starting

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Lu et al. 3
from the available literature data. The present model offers an
elegant method for preparing balances for widely varying flue
gas characteristics and operating parameters.
Adsorption mechanism
Adsorption is exothermic. During flue gas cooling the adsorption
equilibrium gradually becomes more favorable, i.e. the equilib-
rium fractional surface coverage continuously increases (Yan
et al., 2006). Donghoon et al. (1999) and Everaert et al. (2003)
described this temperature effect as a function of:
•• Atotal, the total number of adsorption sites per gram of AC
(mol g−1)
•• As, the number of available adsorption sites (mol g–1)
•• T, temperature (°C)
•• ηa an empirical temperature-dependent parameter.
Inoue et al. studied the adsorption of 1,2,3,4-tetrachlorobenzene,
a dioxins surrogate, on different kinds of AC (Inoue and
Kawamoto, 2005). For two types, with specific surface area of
1213 and 590 m2 g−1, respectively, these temperature effects were
expressed as: q = α × 10–0.013T and q = α × 10–0.012T ; q is the equi-
librium adsorption amount (mg g−1) and α depends on the AC
characteristics. These temperature effects are averaged as:
q = α × 10-0.0125T (1)
The steady-state concentration of organic pollutants in incinera-
tor flue gas has been estimated at 100 µg Nm−3 (Inoue and
Kawamoto, 2005; Karademir et al., 2004), although such values
are influenced by plant operation and quality, combustion set-
ups, and ill-mixed waste. For this concentration of 100 μg Nm−3
the equilibrium adsorption amount (at 170 °C) calculated by the
adsorption isotherms proposed by Inoue and Kawamoto (2005)
can be expressed as a function of specific surface area (Figure 2):
q = 0.0086SSS
Equations (1) and (2) allow the equilibrium amount adsorbed q
(mg g−1) to be expressed as a function of specific surface area SSS
(m2 g−1) and temperature:
0.0086 S SS
q= ´10 -0.0125T
10-0.0125170
´
The number of available adsorption sites As (mol g−1) follows
from Equation (3), taking into account the molecular weight of
1,2,3,4-Tetrachlorobenzene:
As = 5.31 × SSS × 10−0.0125T − 6
The adsorption of dioxins by fly ash is related to the presence
of residual carbon in fly ash, with mineral material adsorbing less.
The carbon content of fly ash is typically 2 to 5% (Stanmore,
2004). Gao et al. (2010) studied samples from fluidized bed and
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Figure 2.  Equilibrium amount adsorbed q (mg g−1) as a
function of specific surface area SSS (m2 g−1) for eight types of
activated carbon. Least square fit: q = 0.0086SSS
stoker incinerators, with residual carbon content and specific sur-
face area of, respectively 1.24%/5.9 m2 g−1; 2.56%/7.2 m2 g−1.
Therefore, if the specific surface area of fly ash is entirely in resid-
ual carbon, then its specific surface area attains 476 m2 g−1 and
281 m2 g−1, respectively, assuming that all adsorption takes place
by residual carbon, equivalent to AC with an average specific sur-
face area of 378 m2 g−1. This value compares conservatively with
that of 450 ± 150 m2 g−1, found by Birnbaum et al. (1997).
If Adust (mol g−1) represents the available adsorption sites of
incinerator fly ash and ϕresidual-carbon the mass fraction of carbon in
fly ash, then Adust is given by:
Adust = ϕ residual-carbon × 5.31 × 378 × 10−0.0125T − 6
(5)
= 2ϕ residual-carbon × 10−0.0125T − 3
Lime features almost the same number of adsorption sites as fly
ash (Donghoon et al., 1999); its contribution is assumed equiva-
lent to that of fly ash with carbon content 0.5%, so that the total
(2) number of available adsorption sites can be combined to:
Aa = 2ϕ residual-carbon × 10−0.0125T − 3 Cdust + 10−0.0125T − 5 Clime
(6)
+ 5.31 × SSS × 10−0.0125T − 6 CAC
where Cdust, Clime, CAC are the concentrations (g Nm−3) of fly ash,
(3) lime and AC, respectively.
Although AC effectively adsorbs dioxins, equilibrium data
has rarely been reported: indeed, it is difficult to generate vapour
phase dioxins steadily and control concentrations in a range from
parts-per-thousand to parts-per-billion, as in actual incinerator
flue gas (Yang et al., 1999).
(4) Adsorption of dioxins can best be described by the semi-
theoretical model proposed by Donghoon et al. (1999) and
Everaert et al. (2003):
dCPCDD/F
= − ki Aa CPCDD/F (7)
dt
4 Waste Management & Research 0(0)

where CPCDD/F is the dioxins concentration in flue gas (ng where tBF is its cleaning cycle time (min), Sfiltration is the filtration
TEQ Nm−3), t is the time (s), ki is the adsorption coefficient area of the baghouse filter (m2), Q is the flue gas flow rate (Nm3 h−1).
(Nm3 mol−1 s−1) and Aa is the number of available adsorption Inserting Equations (11) and (12) into Equation (10) yields:
sites (mol Nm−3).
They define dioxins removal efficiency ηi as:  − k2 Aa2 fs1800ε × 
ηf = 1 − exp  
 ( Cdust + Clime + CAC ) × tBF / 60 
(13)
C −C
ηi = 0 = 1 − exp ( − ki Aa t ) (8) As
C0
Aa2 ( Cdust + Clime + CAC ) = Aa
with C0, C (ng TEQ Nm−3) the initial and final dioxins concentra- (14)
tions in flue gas.
ηf becomes:

ηf = 1 − exp ( −k2 Aa fs1800ε × tBF / 60 ) (15)

Adsorption model for entrained flow
Adsorption efficiency ηt in entrained flow can now be expressed
using the adsorption coefficient k1 (Nm3 mol−1 s−1), and contact
time tt (s) in entrained flow.
Combining Equations (6) and (8) yields:
  2ϕ residual-carbon × 10−0.0125T − 3 Cdust  
 
η t = 1 − exp −k1  +10−0.0125T − 5 Clime
  −0.0125T − 6
  +5.31 × SSS × 10 CAC  
Donghoon et al. (1999) fitted a value of 9200 Nm3 mol−1 s−1
for k1. Taking into account the value of As and that in Everaert
et al. (2003) a value of 275 395 Nm3 mol−1 s−1 was selected
for k1.
Adsorption model for filter cake
The adsorption efficiency for filter cake can be expressed as
(Everaert et al., 2003):
ηf = 1 − exp ( −k2 ( ρ b × 1000 ) Aa2 fstf )
where ηf is the adsorption efficiency of filter cake, k2 is the
adsorption coefficient in the filter cake (Nm3 mol−1 s−1), ρb is
the bulk density of filter cake (kg m−3), Aa2 is the number of
available adsorption sites in filter cake (mol g−1), fs is the
fraction of unoccupied adsorption sites of adsorbents in filter
cake (–).
The residence time tf of flue gas in filter cake (s) is:
dε
tf =
vf
The fraction of unoccupied adsorption sites of adsorbents in filter
cake fs represents:
Cinlet × η t / 109
fs = 1 −
 2ϕ residual-carbon × 10−0.0125T − 3 Cdust 
 
322 ×  +10−0.0125T − 5 Clime  (16)
 
 +5.31 × SSS × 10
−0.0125T − 6
CAC 
 
 tt  (9)
 
where Cinlet the dioxins concentration at the inlet of ACI + BF
system (ng Nm−3). Competitive adsorption by polychlorinated
biphenyls (PCBs), or PAHs, however, is ignored.
According to engineering experience, the parameters in
Equation (16) are estimated as: Cinlet, 1 ng TEQ Nm−3; ηt, 0.8;
ϕresidual-carbon, 3.5%; Cdust, 3 g Nm−3; Clime, 3 g Nm−3; CAC, 0.1 g
Nm−3; T, 180 °C; and Sss, 850 g m−2.
Then fs is calculated as 99.99%. In actual industrial processes,
this value will vary with that of all the other parameters. Actually,
fs is so close to 1 that the system uses AC at an efficiency of <3%
(Kim et al., 2007).
The available adsorption sites in filter cake, Aa2 is:
(10)
Aa2 = 2ϕ residual-carbon × 10−0.0125T − 3 f D + 10−0.0125T − 5 f L
(17)
+ 5.31 × SSS × 10−0.0125T − 6 f AC
with fD, fL, and fAC, the mass fraction of fly ash, lime, and AC in
filter cake, respectively.
The adsorption coefficient in filter cake k2 is still unknown. A
value of 79.1 Nm3 mol−1 s−1 follows from fitting experimental
results from (Chi and Chang, 2005; Chi et al., 2005, 2006a,
2006b). This value is based on limited data, however, and does
not necessarily apply to other conditions.
(11)
Thus, the adsorption efficiency of filter cake becomes:

where d is the thickness of filter cake (m), ε is its void fraction   2ϕ residual-carbon  
(about 0.5), vf the filtration velocity (m s−1).   −0.0125T − 3  
  ×10 fD  
The thickness of filter cake d can be expressed as:  dε 
ηf = 1 − exp  −79.1( ρ b × 103 ) fs  +10−0.0125T − 5 f L   (18)
v
  +5.31 × SSS  f 
0.5Q × ( Cdust + Clime + CAC ) × tBF/60    
d= (12)   ×10−0.0125T − 6 f AC  
ρ b × Sfiltration    

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Lu et al. 5

Removal efficiency of vapour phase
dioxins ηg by the ACI + BF system
Removal of the vapour phase dioxins proceeds in two steps: (1)
entrained flow and (2) filter cake adsorption. Hence:
1 − ηg = (1 − η t ) (1 − ηf )
where ηg is the removal efficiency of vapour phase dioxins by the
ACI + BF system.
Total removal efficiency of vapour phase
and particle bound dioxins η
Particle bound dioxins may vary from 15 to 85% of total dioxins
in flue gas (Everaert and Baeyens, 2002; Everaert et al., 2003).
Ideally, they are all eliminated by filtration. There is no evidence
that desorption of dioxins follows particle collection.
A modern incinerator plant produces low adsorptive fly ash,
with < 1 wt.% residual carbon and typically > 80% of dioxins in
the gas phase. Conversely, obsolete plant shows poor burnout,
with typically 3–10 wt.% residual carbon in fly ash and 70–85%
of dioxins in particulates. Thus, particulate burnout is determin-
ing gas/particulate (G/P) distribution.
Assuming that the percentage of particle bound dioxins is ϕs
at the inlet of the ACI + BF system, then total removal efficiency
of vapour phase + particle bound dioxins can be expressed by:
η = ϕsηs + (1 − ϕs )ηg
with η the total removal efficiency of the vapour phase and parti-
cle bound dioxins, and ηs is the removal efficiency of particle
bound dioxins by filtration.
Modelling individual congeners
The removal efficiency of each congener can be calculated by
Equation (20), but before the partitioning between vapour phase
and particle bound (or ϕs) should be known. Major parameters
affecting this partitioning include: vapour pressure, particle con-
centration, and upstream APCD. Chi and Chang (2005) described
the available results by:
C   c 
log  v  = mlogPLO + log   (21)
 Cs   PM 
where Cv and Cs are the concentrations of dioxin congeners pre-
sent in the vapour phase and adsorbed on particles (ng Nm−3),
respectively, PLO is the saturation vapour pressure of a dioxin
congener (Pa), PM is the particulate matter concentration in flue
gas (mg Nm−3), m is a parameter dependent on the type of
upstream APCDs, c describes the particulate matter in flue gas,
(19)
and the values of m and c depend on the type of APCDs applied
upstream of the adsorption treatment, as shown in Table 2.
The vapour pressures of PCDD/F congeners increase with ris-
ing temperature. LogPLO can be expressed as (Chi and Chang,
2005; Eitzer and Hites, 1988, 1998):
−1.34 ( RI )
logPLO = + 1.67 × 10−3 ( RI )
T + 273.15
1320 (22)
− + 8.087
T + 273.15
where RI is the retention index (Donnelly et al., 1987; Hale et al.,
1985).
For 2,3,7,8-substituted PCDD/F congeners RI varies from
2338 to 3196 (Chi and Chang, 2005). Their removal efficiency
can be calculated from Equation (23) as:
ηcongener,i = ϕs,i × ηs,i + ϕ v,i × ηg,i (23)
where ηcongener,i is the removal efficiency of each particular con-
gener, ϕs,i and φv,i are the percentages of the particle bound part
and vapour phase part for each congener at the inlet of ACI +
(20) BF system, ηs,i and ηg,i are the removal efficiencies of particle
bound and vapour phase dioxins, for each congener.
The value of ϕs,i and ϕv,i can be obtained from Equations (21)
and (22). The ηs,i values are closely grouped and resemble the
removal efficiency of particulates by BF (Chi and Chang, 2005;
Chi et al., 2006b); hence ηs,i is estimated in agreement with the
particulates removal efficiency, for example, 0.999. The removal
efficiency of each congener i in the vapour phase ηg,i is related to
its chlorination level; the adsorption coefficient of each congener
(k1,i and k2,i) decreases with rising chlorination (Chi and Chang,
2005; Chi et al., 2006b). Assuming that the adsorption coeffi-
cients of the congeners in entrained flow and filter cake are,
respectively:
k1,i = ξi × k1 (24)
k2 ,i = ξi × k2
(25)

Table 2.  Dioxins partitioning parameters –Equation (21) (n = 238) (Chi and Chang, 2005).

APCD applied upstream m c Standard deviation

None 1.11 ± 0.022 0.042 ± 0.005 ± 0.133 (n = 34)
Cyclone (CY) 0.853 ± 0.019 62.8 ± 11.7 ± 0.086 (n = 34)
Electrostatic precipitator (ESP) 0.606 ± 0.014 0.981 ± 0.182 ± 0.064 (n = 34)
Activated carbon fixed bed (AC-FB) 0.568 ± 0.013 409 ± 76.9 ± 0.086 (n = 34)
Selective catalytic reduction (SCR) 0.459 ± 0.010 0.133 ± 0.034 ± 0.096 (n = 34)
Activated carbon injection (ACI) + baghouse filter (BF) 0.689 ± 0.015 2.62 ± 0.451 ± 0.111 (n = 68)

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6 Waste Management & Research 0(0)

where k1,i and k2,i, respectively, representing the adsorption

coefficients of the congeners in entrained flow and filter cake, ξi
is the ratio of k1,i and k1, k2,i and k2 for each congener, which will
show the adsorption efficiency difference for the congeners with
different chlorination levels.
The values of ξi for 17 toxic 2,3,7,8-substituted PCDD/F con-
geners were obtained by fitting experimental results from the lit-
erature (Chi et al., 2005), as shown in Table 3.
These values of ξi were obtained by fitting very limited exper-
imental literature data. Collecting further data will establish these
more precisely.
Figure 3.  Comparison of model predictions and experimental
results of Tejima et al. (1996)
Validation of the model
Validating the model requires values for dioxin concentrations
at the inlet and outlet of the ACI + BF system, and for all
parameters in Equations (9) and (18). Tejima et al (1996) pro-
vide most parameter values, except for Clime = 3 g Nm−3, tt = 2
s, ϕresidual-carbon = 3.5%. AC is injected at CAC = 150 mg Nm−3. ϕs
is derived from Chi and Chang (2005), Chi et al. (2006a), and
Chi et al. (2006b), and the value of ηs is approximated by the
fly ash removal efficiency of BF. Figure 3 shows our model
calculations are well in line with the experimental results of
Figure 4. Effect of temperature. Parameter values: fly ash
Tejima et al. (1996), which effectively proves the validation of
concentration, 3g Nm−3; residual carbon in fly ash, 3.5%; lime
this model. concentration, 3 g Nm−3; residence time in of entrained flow,
2 s; specific surface area of AC, 850 m2 g−1; thickness of filter
cake, 2 mm; bulk density of filter cake, 500 kg m−3.
Factors of influence
The mechanisms for removing particle bound and vapour phase Particle bound dioxins are retained together with particulate
dioxins are essentially different: vapour phase dioxins transfer to matter. Studies indicate that their removal efficiencies are fairly
AC or other particles and are retained thereupon. close (Chi and Chang, 2005; Chi et al., 2006b). As the removal
At usual temperatures for BF operations the adsorption of efficiency of fly ash by BF normally exceeds 99.9%, virtually all
dioxins is still strong and presumably determined by the quality solid-phase dioxins should be removed by BF.
of gas/particle contact; namely external mass transfer. Conversely,
most sorption capacity resides in internal pore area.
Effect of temperature
Temperature strongly influences the adsorption of dioxins on AC,
Table 3.  The values of ξi for 17 toxic 2,3,7,8-substituted
PCDD/F congeners. because (1) vapour pressure rapidly increases with rising tem-
perature, so that more dioxins report to the vapour phase (Rordorf,
Congener ξi 1989), and (2) adsorption is exothermic and fractional surface
2,3,7,8-TCDD 1.370 coverage decreases with rising temperature.
1,2,3,7,8-PeCDD 1.231 The effect of temperature on ηg is shown in Figure 4, based on
1,2,3,4,7,8-HxCDD 1.116 model calculations. The decrease in adsorption is most marked at
1,2,3,6,7,8-HxCDD 0.865 higher temperature, with an inflection point between 200 and 250
1,2,3,7,8,9-HxCDD 0.973 °C; ηg decreases from 0.982 to 0.616 while temperature increases
1,2,3,4,6,7,8-HpCDD 0.933
from 150 to 200 °C, at a (low) AC dosing rate of 50 mg Nm−3.
OCDD 0.862
2,3,7,8-TCDF 1.072 Therefore, operating temperature should not much exceed 150 °C, a
1,2,3,7,8-PeCDF 1.227 typical temperature of spray absorbers. Nevertheless, baghouse tem-
2,3,4,7,8-PeCDF 0.968 perature must never decrease to < 130 °C to avoid deliquescence of
1,2,3,4,7,8-HxCDF 1.069 hygroscopic salts (CaCl2 mainly) leading to considerable corrosion
1,2,3,6,7,8-HxCDF 1.102 and clogging.
2,3,4,6,7,8-HxCDF 0.984
1,2,3,7,8,9-HxCDF 0.995
1,2,3,4,6,7,8-HpCDF 1.050 AC dosing rate
1,2,3,4,7,8,9-HpCDF 0.974
Figure 5 shows the effect of AC dosing rates on ηg: the value of
OCDF 0.813
ηg increases linearly up to 65 mg Nm−3, but is only slightly

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Lu et al. 7
Figure 5.  Effect of AC dosing rate. Parameter values: fly ash
concentration, 2 g Nm−3; residual carbon content of fly ash,
3.5%; lime concentration, 3 g Nm−3; residence time in entrained
flow, 2 s; specific surface area of AC, 850 m2 g−1; thickness of
filter cake, 2 mm; bulk density of filter cake, 500 kg m−3.
affected once this rate exceeds 150 mg Nm−3. Those modelling
results are in line with Chang et al. (2009). According to
Equations (9) and (18), the relationship between adsorption effi-
ciency (ηt and ηg) and AC dosing rate is an exponential function,
which leads to dwindling effects of adsorption with increasing
AC concentration.
Moreover, ηg almost attains unity, when the AC dosing rate
reaches 200 mg Nm−3. This rate corresponds to the average prac-
ticed in Germany, where much lignite cokes is used, with mark-
edly lower specific surface area. Kim et al. (2007) found that ηg
even decreased with rising AC dosing rate for > 300 mg Nm−3,
because of the rising pressure drop over BF. Therefore, a maxi-
mum dosage of 200 mg Nm−3 is recommended and higher rates
will merely waste AC. For other operating conditions, or differ-
ent qualities of AC, hydrated lime, or fly ash, the optimum dos-
age may be different.
The cost of AC consumption depends on (1) dosing rate and
(2) unit cost. In principle, dosage rates should be selected so that
the probability and frequency of exceeding the limit value
remains marginal. In some countries, however, the penalty of
exceeding limit values is harsh (Baert et al., 2002), so that most
operators prefer a ‘no risk’ approach. A sensible strategy is to
maintain a thrifty rate of 50 mg Nm−3 and not to exceed 200 mg
Nm−3. The preferred dosing rate can be finely tuned on a basis of
(a) operating temperature and (b) occurrence of combustion
upsets with their associated, yet delayed dioxins peak values in
the flue gas.
Adsorbent characteristics
Grain-size, pore structure, and specific surface area all exert an
important influence on the adsorption power.
Effect of grain size.  At the same dosing rate the dioxins
removal efficiency for 28 µm (grain size) pulverized lignite
cokes is more than twice that at 63 µm, following pilot tests
(Wirling and Esser-Schmittmann, 2001). The external surface
Sext rises with a factor of 63/28 when shifting to finer powder
at similar dosing rates, suggesting control by external diffu-
sion. The tests were conducted, however, with toluene as
surrogate.
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Figure 6.  Effect of AC specific surface area. Parameter values:
fly ash concentration, 3 g Nm−3; residual carbon content of fly
ash, 3.5%; lime concentration, 3 g Nm−3; AC concentration, 50
mg Nm−3; residence time in entrained flow, 2 s; thickness of
filter cake, 2 mm; bulk density of filter cake, 500 kg m−3.
Effect of pore structure.  Chi et al. (2006b) indicated the sur-
face area of mesopores + macropores (2~20 nm) as the key factor
determining adsorption capacity for dioxins. This capacity lin-
early increases with surface area of mesopores + macropores
(2~20 nm). However, adsorbed dioxins bear no significant rela-
tionship with micropore surface area (Chi et al., 2006b), suggest-
ing control by internal diffusion.
Inoue and Kawamoto (2005) found for 1,2,3,4-tetrachlo-
robenzene that micropore (pore diameter < 2 nm) volume gov-
erned adsorption capacity for adsorbents such as AC, activated
coke, and carbonized wood: their specific surface area increased
linearly with micropore volume, and adsorption capacity
increased almost linearly with micropore volume and specific
surface area.
Thus, the surface area of mesopores + macropores (2~20 nm)
is a key factor determining the adsorption capacity of AC for
dioxins, while the micropore volume (pore diameter < 2 nm) is
more important for 1,2,3,4-tetrachlorobenzene. Possibly, such
dissimilarities relate to different molecular sizes of dioxins and
1,2,3,4-tetrachlorobenzene. Hence, external mass transfer, inter-
nal mass transfer, or specific surface all may control adsorption,
depending on the case.
Specific surface area of AC.  Model calculations are based on
the hypothesis that the number of available adsorption sites is
proportional to the specific surface area. In Figure 6 ηg slowly
increases with specific surface area of AC as an almost straight
line with low slope, yet increasing with rising temperature.
Therefore, at high operating temperatures ηg increases more sig-
nificantly than at lower temperature.
Residence time during entrained flow
The effect of residence time during entrained flow on adsorp-
tion efficiency ηt was investigated by Wirling and Esser-
Schmittmann (2001) using toluene tracers. Figure 7 shows ηt
increasing with increasing residence time, linearly at the start,
yet slowing down for longer residence times when ηt tends
towards an asymptotical limit value. The optimum residence
time was much larger at higher than at lower temperatures.
Therefore, in industrial processes appropriate residence times
8 Waste Management & Research 0(0)
Figure 7.  Effect of residence time. Parameter values: fly ash
concentration, 3 g Nm−3; residual carbon content of fly ash,
3.5%; lime concentration, 3 g Nm−3; AC concentration, 50 mg
Nm−3; specific surface area of AC, 850 m2 g−1.
Figure 8.  Effect of fly ash concentration. Parameter values:
lime concentration, 3 g Nm−3; AC concentration, 0 mg Nm−3;
residence time in entrained flow, 2 s; thickness of filter cake,
2 mm; bulk density of filter cake, 500 kg m−3.
should be selected, depending on operating temperature, space
requirements, and dosage.
Fly ash concentration
Figure 8 shows ηg in the extreme case of no AC injection, while
the particulate carbon in fly ash is considered.
Adsorption of dioxins by fly ash is still important in two
cases: low temperature and/or high fly ash content. Fluidized bed
fly ash attains concentration values between 20 and 30 g Nm−3.
Figure 8 shows that ηg may reach values of 0.777–0.998; namely
a high removal efficiency, even without injecting any AC. Yet,
once the fly ash concentration reaches elevated levels, ηg is less
affected and tends to a stable limit value.
In comparison with the fluid bed case, mechanical grate
units show much lower dust loadings, typically of 3~5 g Nm−3.
This lower load has a considerable effect, as can be seen from
Figure 8.
Residual carbon in fly ash
Higher residual carbon in fly ash relates to less complete com-
bustion. As a consequence, the concentration of products of
incomplete combustion (PICs) in flue gas will become higher, so
that this situation should be avoided. Yet, it also has a positive
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side: residual carbon in fly ash increases its adsorption capacity
for dioxins. Especially in the case of fluidized bed incineration,
with its high fly ash concentrations in flue gas, this decisively
affects dioxins adsorption and removal.
Figure 9 shows the calculated effect of residual carbon con-
tent on ηg.
For mechanical grate plant the value of ηg doubles when the
carbon content increases from 0.5 to 2.5%; ηg even reaches 0.8
when the carbon content attains 5% and exceeds 0.95 when it
attains 10%. For fluidized bed incinerators, ηg already reaches
0.96 for a carbon content of only 2%. Hence, the contribution of
fly ash to dioxins adsorption can be significant and should be
fully exploited, without resorting to poor combustion
conditions.
Parameters outside the model
Pressure drop over the BF and fly ash concentration at the
outlet of the BF.  Fly ash concentration at the outlet of the BF
rises very slowly with pressure drop, yet rises rapidly when pres-
sure drop exceeds 20 cm water column (wc) (Kim et al., 2007).
Hence, the usual practice features 14 cm wc for clean bags and
18 cm wc as signal for cleaning. Dioxins emissions usually climb
linearly with fly ash concentration at the BF outlet. Therefore, fly
ash concentrations at the outlet of BF should always remain
< 10 mg Nm−3 (Kim et al., 2007). The latter corresponds to 10 pg
Nm−3 in cases in which the dust load is 1 ng I-TEQ g−1, yet it
attains the emission limit in cases in which this load reaches
10 ng I-TEQ g−1.
Effect of the dioxin congeners distribution.  Removal effi-
ciency of dioxin isomer groups, ηi, by means of fixed bed drops
with rising chlorination level (Karademir et al., 2004), low
chlorinated congeners representing a larger fraction of vapour
phase dioxins (Lin et al., 2008) and activated carbon having no
effect on particle bound dioxins. Removal efficiency of dioxin
isomers in the vapour phase using an ACI + BF system (ηgi)
also falls with rising chlorination (Chi et al., 2006b; Chi and
Chang, 2005).
Conclusions
This paper expands the classical Everaerts–Baeyens model for
predicting dioxins removal efficiency from flue gas by proposing
fs, the fraction of free adsorption sites in adsorbents retained in
filter cake and modulating the contribution of fly ash to dioxins
adsorption according to its residual carbon content. The model
also accounts for G/P partitioning of dioxins and it predicts diox-
ins removal efficiency for each congener separately.
The various parameters that affect adsorption of dioxins from
flue gas have been analysed and the effect of operating tempera-
ture, AC dosing rate, adsorbent characteristics (grain-size, pore
structure, and specific surface area), entrained-flow contact time,
fly ash concentration, and residual carbon content, and type of
incinerator (stoker or fluidized bed) are illustrated under realistic
operating conditions. Using high AC injection rates is both more
Lu et al. 9
Figure 9.  Effect of residual carbon content of fly ash. Parameter values: fly ash concentration for fluidized bed incinerator and
mechanical grate incinerator are 25 g Nm−3 and 3 g Nm−3, respectively; lime concentration, 3 g Nm−3; AC concentration, 0 g Nm−3;
the temperature, 170 °C; residence time in entrained flow, 2 s; thickness of filter cake, 2 mm; bulk density of filter cake, 500 kg m−3.
expensive and less effective than monitoring incinerator condi-
tions and acting appropriately in the case of combustion set-ups.
Funding
This work was supported by the National State Basic Research
Program of China (973 program, 2011CB201500), National High
Technology R&D Key Program of China (2012AA062803), Major
Science and Technology Program for Water Pollution Control and
Treatment (2009ZX07317-003), Zhejiang University Y. C. Tang
Disciplinary Development Fund, and Program of Introducing Talents
of Discipline to University (No. B08026).
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