Brazilian Journal

of Chemical
Engineering

ISSN 0104-6632
Printed in Brazil
www.abeq.org.br/bjche

Vol. 32, No. 01, pp. 87 - 97, January - March, 2015

dx.doi.org/10.1590/0104-6632.20150321s00003163

FORMATION OF DIOXINS AND FURANS DURING

MUNICIPAL SOLID WASTE GASIFICATION
E. J. Lopes1*, L. A. Okamura2 and C. I. Yamamoto1
1

Federal University of Paran, Rua XV de Novembro 1299, Curitiba - PR, Brasil.

Phone: + (55) (41) 9147-9828, Fax: + (55) (41) 3205 0016, www.ufpr.br
*
E-mail: evandro@elbrasil.com.br; E-mail: citsuo@gmail.com
2
Federal Technology University of Paran, Curitiba - PR, Brasil.
E-mail: layokamura@yahoo.com.br

(Submitted: December 10, 2013 ; Revised: March 14, 2014 ; Accepted: May 23, 2014)

Abstract - Thermal treatment is an interesting strategy to dispose of municipal solid waste: it reduces the
volume and weight of the material dumped in landfills and generates alternative energy. However, the process
emits pollutants, such as dioxins and furans. The present study evaluated MSW gasification-combustion
integrated technologies in terms of dioxin and furan emission; and compared the obtained data with literature
results on incineration, to point out which operational features differentiate the release of pollutants by these
two processes. The results show that the process of integrated gasification and combustion emitted 0.28 ng N-1
m-3, expressed in TEQ (Total Equivalent Toxicity), of PCDD/F, less than the maximum limits allowed by
local and international laws, whereas incineration normally affords values above these limits and requires a
gas treatment system. The distinct operational conditions of the two thermal processes, especially those
related to temperature and the presence of oxygen and fixed carbon, led to a lower PCDD/F emission in
gasification.
Keywords: Gasification; Municipal Solid Waste; Pollutants; Dioxins; Furans.

INTRODUCTION
The dibenzo-p-dioxins (PCDDs) and the polychlorinated dibenzofurans (PCDFs) constitute a group
of persistent pollutants that inexorably originate from
thermal and combustion operations (Altarawneh et
al., 2009). The chemical and toxicological properties
of these compounds rely primarily on the number
and position of chlorine atoms bound to the two
aromatic rings (Altarawneh et al., 2009). Certain
dioxin and furan isomers are well known for their
toxicological featuresthey exert carcinogenic and
mutagenic effects. One classic example is the dioxin
isomer with chlorine substituents in positions 2, 3, 7,
and 8, or 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD),
which is among the worlds most toxic substances
*To whom correspondence should be addressed

(Huang and Buekens, 1996; Assuno and Pesquero,

1999).
PCDD/PCDF emissions from incineration processes were first detected in 1977 (Olie et al., 1977).
Since then, scientists have assessed this type of
emission by an array of thermal processes that also
involve integrated gasification and combustion processes (Huang and Buekens, 1996). The release of
dioxins, furans, and other pollutants during waste
incineration accounts for its environmentally negative reputation (Cunliffe and Williams, 2009). Once
PCDDs and PCDFs enter the atmosphere, they are
subject to chemical, physical, and biological transformations, ultimately contaminating the soil, water
bodies, and sediments (Martens et al., 1998).
In Brazil, where the present study takes place, the

88

E. J. Lopes, L. A. Okamura and C. I. Yamamoto

organization which is responsible for establishing

national norms and standards of pollution control is
CONAMA (Conselho Nacional do Meio Ambiente
National Council of the Environment). It established that dioxin and furan emissions can not exceed
0,5 ng TEQ/Nm3 during thermal treatment of waste.
The present paper assessed the municipal solid
waste (MSW) gasification in a horizontal chamber,
with post-combustion of the generated gases, in
terms of the dioxins and furans emitted along with
combustion gases. To this end, the MSW will be
transported through a mobile grit gasifier coupled to
a torsional combustion chamber. We will compare
the results with literature data on the incineration
process, to find out which operational features differentiate dioxin and furan emission by these two
processes, incineration technology and gasificationcombustion technologies.
Incineration and Gasification
Industrialized nations generally employ incineration/combustion and gasification to generate energy
and to treat waste (Tabasov et al., 2012). The current lack of landfills or even their closure has made
solid waste treatment by thermal processes an attractive strategy. Moreover, both gasification and incineration reduce waste mass and volume, destroy hazardous residues, and recover energy (Martens et al.,
1998).
It is possible to achieve energy recovery by reusing heat, producing electric energy, or generating
alternative fuels by the Fisher-Tropsch process
(Tabasov et al., 2012). Nevertheless, thermal MSW
treatment poses some drawbacks: it releases air pollutants together with the combustion gases, the ashes
contain hazardous compounds, and the water used in
some specific points of the equipment becomes contaminated.
Incinerators and gasifiers designed to treat waste
have to meet the restrictive requirements of environmental agencies and are always subject to intense
monitoring. It is sometimes necessary to install gas
treatment systems, which require high investment
(Alencar Jnior and Gaba, 2001).
Gasification technology has been widely applied
to produce chemicals and fuels. Current trends in the
chemical and oil industry point to the growing use of
this process to obtain synthesis gas. This is happening for two main reasons: (1) gasification furnishes a
consistent and high-quality gas, and (2) a large variety of materials can feed the system (Orr and Maxwell,
2000).
During gasification, partial oxidation at high tem-

perature (between 773 and 1673 K) and variable

pressure (from 105 to 33.105 Pa) convert biomass, or
any solid or liquid carbonaceous fuel, into a high-energy gas (Morrin et al., 2011); most of the feedstock
thermally decomposes into the gas. Unfortunately,
small amounts of sub-products also originate during
the process, including tar, coal, and ash (Cohce et al.,
2011). Gasification involves endothermic chemical
reactions that demand heat and generate carbon
monoxide (CO), hydrogen (H2) and other compounds. Depending on the reactor design and operational conditions, the process also affords methane
and hydrocarbons (Singh et al., 2011).
There are two types of gasification processes, a
direct one and another indirect. In direct gasification,
also known as auto-thermic, the process occurs in a
single reactor, where the exothermal oxidation of the
carbon takes place. Direct gasifiers normally operate
using air or oxygen as oxidizing agents. In this case
the heat necessary for the process is produced inside
the reactor (Vitasar et al., 2011), since the oxidation
reactions provide the energy to maintain the high
temperature of the process (Belgiorno et al., 2003).
In the indirect process, known as allothermic, the
gasification occurs with an external energy source.
Water vapour is used as the most common gasifying
agent; it is easily produced and increases the amount
of hydrogen in the produced gas by reforming (Singh
et al., 2011).
The gasifiers, in which the gasification process
occurs, are classified according to the following factors
(Moura, 2012):
I. Calorific heat of the product gas (low up to 5
MJ/Nm3; medium from 5 to 10 MJ/Nm3; or high
from 10 to 40 MJ/Nm3);
II. Type of gasifying agent (air, steam, oxygen or
hydrogen);
III. Movement direction of the feeding material
and gasifying agent (updraft, downdraft; crossdraft or fluidized bed);
IV. Operational pressure (atmospheric or pressurized up to 6 MPa);
V. Feeding material (industrial waste, municipal
solid waste, biomass/wood).
Usually the gasifiers are internally made from refractory material, covering the combustion zone or
even the whole gasification chamber, to protect the
metallic parts and avoid the loss of energy by heat
exchange. The most used and known gasifiers are the
fluidized bed reactor and the fixed bed reactor.
During incineration, solid waste burns and directly generates thermal energy. As for gasification,
the waste is first transformed into a gaseous product
with enough heat power to produce thermal, me-

Brazilian Journal of Chemical Engineering

Formation of Dioxins and Furans During Municipal Solid Waste Gasification

chanical (engines), or electric energy (Tanigaki et al.,

2012).
Waste incineration is one of the most frequently
employed technologies to process waste thermally
and it can be applied to several types of materials.
This process occurs under an excess of oxygen, to
ensure complete oxidation. MSW incineration can
reduce up to 90 and 75% of the initial waste volume
and weight, respectively (Tabasov et al., 2012).
Research into dioxin and furan formation has targeted MSW incineratorselevated dioxin concentrations occur in the fly ash and gas flow during the
incineration process (Huang and Buekens, 1996).
Dioxin and Furan Formation
Dioxin and furan generation is a complex phenomenon that involves multiple solid- and gas-phase
reactions between minimum amounts of reagents.
During thermal waste destruction, dioxins and furans
are known to arise together with combustion gases,
fly ash, and even slag (McKay, 2002).
Researchers have examined two main hypotheses
regarding the mechanism of PCDD and PCDF formation during combustion, namely the De Novo
Synthesis (PCDD/PCDF production from elemental
carbon) and dioxin and furan generation from precursors. These hypotheses are not exclusive; indeed,
they may take place simultaneously during burning
of the carbonaceous material (A.J. Chandler and
Associates Ltd., 2006).
The mechanisms of PCDD/PCDF generation
during combustion remain uncleartheir concentration is low, so their quantification requires complex
analytical instruments and a continuous analytical
method that provides real-time information (Cunliffe
and Williams, 2009). What is known is that dioxins
and furans originate via not yet clarified homogeneous and heterogeneous routes.
The homogeneous route is the most probable
source of these pollutants inside the combustion
chamber; this route involves gas-phase reactions of
chlorinated organic precursors like chlorobenzenes
and chlorophenols, at higher temperatures (between
673 and 1073 K) (Stanmore, 2002). Even though it is
known that dioxins and furans emerge during combustion, researchers used to believe that the high
temperatures of the incineration oven destroyed
them. However, PCDDs and PCDFs might arise after
the gas flow leaves the combustion chamber; that is,
when the gas goes through an air pollution control
device that operates at lower temperatures (between
473 and 763 K) (Dwel et al., 1990; Reis, 2009).

89

Heterogeneous reactions account for dioxin and

furan formation in the post-combustion region. They
comprise two reaction pathways: (1) The de novo
synthesis, in which the carbonaceous matrix burns
with simultaneous oxidation and chlorination. Low
oxygen concentrations (less than 2%) may diminish
the rate of PCDD/PCDF production via the de novo
synthesis (Stanmore, 2002). (2) Assisted catalytic
coupling of the precursorsincomplete organic waste
combustion in the incinerators culminates in organic
fragments that can further serve as precursors of
dioxin and furan molecules on the fly ash surface
(McKay, 2002).
Transition metal species, especially copper and
iron, exert a strong catalytic effect on PCDD/PCDF
formation via the two heterogeneous routes (Altarawneh et al., 2009; Cunliffe and Williams, 2009).
Experiments on a lab scale and process modeling
have aided researchers in understanding the mechanisms of dioxin and furan production (Ruuskanen et
al., 1994; Shao et al., 2010; Li et al., 2012).
Briefly, thermal processes produce PCDDs/PCDFs
if the following conditions apply (Huang and Buekens,
1996; Cabrita et al., 2003; Suzuki et al., 2004; Altarawneh et al., 2009):
1. Presence of a fixed carbon source, fly ash, to
enable the de novo synthesis in the post-combustion
or cooling region;
2. Presence of chlorinated compounds, formation
precursors, during combustion and after cooling of
the exhaust gases;
3. Presence of catalysts (e.g., copper and/or iron)
in the fly ash;
4. Oxidizing atmosphere, between 10 and 15%
oxygen, in the cooling region;
5. Process temperatures around 473 and 873 K,
with pollution control equipment operating between
473 and 773 K.
EXPERIMENTAL SECTION
A moving grit gasifier was employed to evaluate
dioxin and furan emission during gasification (Figure
1) (Lopes et al., 2011). The equipment was fed with
municipal solid waste (MSW), to generate and subsequently burn the synthesis gas. The device was fed
manually; the combustion system was controlled
manually, as well. The gasified MSW was provided
by a landfill that receives waste collected from 14
small municipalities of the Brazilian states of Santa
Catarina and Paran, and air was used as gasifying
agent.

Brazilian Journal of Chemical Engineering Vol. 32, No. 01, pp. 87 - 97, January - March, 2015

90

E. J. Lopes, L. A. Okamura and C. I. Yamamoto

Figure 1: Scheme of the equipment (gasifier with the combustion chamber) used in the
process of MSW gasification.
To obtain a syngas with combustible properties
capable of maintaining an auto-sufficient combustible system, rigid control of pyrolysis, gasification
and reforming reactions is necessary. The optimization of each step of the process is made in real time,
according to the responses of the remote sensors,
which are located according to their specificity in
strategic points, where the external interventions can
immediately act on the distortions and interferences
caused mainly by the heterogeneity of the feeding
material.
A gasification system with a horizontal chamber
moved by grits, which presents a differentiated morphology adequate for each function, was designed
for this study in order to reconcile the availability of
reagents and energy in each step. It contemplated
surface area, physical condition, size distribution,
rate of homogeneous scattering, chamber area, pressure run, directed flow, pressure drop, turbulence,
gas velocity, retention time and chamber volume.
The working process conditions are the following:
Sub-stoichiometric environment: Control the
addition of gasifying agent punctually according to
local demand in the reactor, informed by temperature sensors and strategically arranged pressure
sensors.
Temperature range: A gradient of 630 to 680 C,
distributed homogeneously in the processed material.
Working pressures: all gas produced by the
processes of drying, pyrolysis and gasification are
immediately pulled into the posterior chambers by
the difference of pressure.
Carriage rate: Different speeds in the material
movement in each step guarantee a better use of the

internal conditions of the reactor.

In this process there is no storage or treatment of
the combustible gases, because once already in the
gas and superheated state, they can be consumed in
the downstream output of the generator or reactor
where they were produced.
Characterization of Municipal Solid Waste
The MSW fed into the gasifier was grossly
shredded, and no adicional treatment was done. The
gravimetric composition of the MSW is presented in
Table 1 and the characterization of the MSW is
demonstrated in Table 2.
Table 1: Gravimetric composition of MSW gasified
in a moving grit gasifier.
Components
Organic residues
Paper and cardboard
Carton packaging
Plastics
PET
PEAD
PVC
PEBD
PP
PS
Other plastics
Diapers and absorbents
Leather, textiles and wood
Rubber, tires, etc.
Total of combustible waste
Total of inorganic waste (not
combustible)

Brazilian Journal of Chemical Engineering

Gravimetric
composition
%
47.9
16.6
1.9
16.1
1.7
0.7
0.4
8.6
3.3
1.2
0.2
5.4
4.7
0.6
93.2
6.8

Formation of Dioxins and Furans During Municipal Solid Waste Gasification

Table 2: Characteristics of the municipal solid waste

gasified.
Characteristics of MSW
C
H
S
N
O
Cl
H2O
Ashes

% mass MSW
25.95
3.21
0.15
0.10
18.11
0.03
49.08
3.36

The UCV (upper calorific value) of the MSW

used in the gasification was 10149 kJ.kg-1 and the LCV
(low calorific value) was 8693 kJ.kg-1.
Ash Analysis
The characterization and classification of the ash
produced during gasification were performed according to the standards referenced by the Brazilian
Association of Technical Standards (ABNT) and the
Standard methods.
The NBR 10004:2004 (ABNT, 2004a) was used
for the classification of the waste analyzed. For the
solubilized and leached extract experiments NBR
10005 (ABNT, 2004b) and 10006 (ABNT, 2004c),
respectively, were applied.

91

For analysis of the extracts the Standard Methods

for the Examination of Water and Wastewater (APHA
et al., 2005) were employed.
Sample Collection
The method 023 of the United States Environmental Protection Agency (USEPA, 1991) was used
for sample collection and analysis, to determine
polychlorinated dibenzo-p-dioxins and polychlorinated
dibenzofurans from municipal waste combustors.
Combustion gas samples for analysis of dioxins
and furans were collected from the exhaust stack of
gases originated in the synthesis gas combustion
chamber, without any previous treatment.
A total of three samplings were performed; each
sample of exhaustion gases was bubbled in the
impingers with different content for approximately 3
hours. The sampling equipment (Figure 2) contained
a glass fiber filter, a condenser, a trap, and four
impingers the first and the second impingers
contained distilled water, the third was empty, and
the fourth contained silica gel. The impingers were
replaced before each sampling. The samplings were
performed using a system for isokinetic sampling
with dry gas meter, orifice plate and calibrated spitot tube.

Figure 2: Schematic representation of the sampling device used during analysis of dioxins and furans.

Brazilian Journal of Chemical Engineering Vol. 32, No. 01, pp. 87 - 97, January - March, 2015

92

E. J. Lopes, L. A. Okamura and C. I. Yamamoto

The impingers were weighed before and after

sampling, to obtain the mass of condensed water
(combustion gas moisture). To sample dioxins and
furans, a trap was used with 40 g of XAD-2 resin. A
glass fiber filter was also used at the beginning of the
experimental setup, to retain particulates.
Sample Extraction
The extraction of the samples containing dioxins
and furans followed the procedures of the EPA
method 23 (USEPA, 1991). The sample recovery and
extraction were performed as described in Table 3.
Dioxin and Furan Analyses
Dioxins and furans were analyzed according to

the method EPA-023 (USEPA, 1991), using Gas

Chromatography coupled with High-Resolution Mass
Spectrometry (resolution of 1:10000 with a stability of
+5 ppm). Immediately prior to analysis, a 20:l (v/v)
aliquot of the recovery standard solution (from Table
1 of method 23 - USEPA, 1991) was added to each
sample. A 2:1 (v/v) sample of the extract was injected
into the gas chromatograph. Sample extracts were first
analyzed using the DB-5 capillary column to determine the concentration of each isomer of PCDD's and
PCDF's. When tetrachlorinated dibenzofurans were
detected in this analysis, another aliquot of the sample
was analyzed in a separate run, using the DB-225
column to measure the 2,3,7,8 tetra-chloro dibenzofuran isomer. The same analysis was conducted for a
reference solution containing known concentrations of
dioxins and furans, for comparison purposes.

Table 3: Description of the sample recovery and extraction for the dioxin and furan analyses.
Container (storage) Part of the sampling
apparatus

Sample recovery

Sample extraction
Sample was added 100:l of the internal standard solution (a stock standard
solution containing the isotopically
labeled PCDD's and PCDF's concentration acconding to Table 23-1 of
USEPA method 23) to the extraction
thimble containing the contents of the
adsorbent cartridge, the contents of
container 1, and the concentrate from
container 2. Cover the contents of the
extraction thimble with a cleaned glass
wool plug to prevent the XAD-2 resin
from floating into the solvent reservoir
of the extractor. The extraction was
carried out with toluene for 16 hours.
The temperature was adjusted to cycle
3 times per hour. After cooling the
system, the toluene extract and 3
rinses of 10 mL were concentrated (until
10 mL) on a rotary evaporator. The
remaining solution was used to perform the chromatographic analysis.

Container 1

Filter

The filter, the particulate matter and

the filter fibers which adhere to the
filter holder gasket were carefully transferred to a soxhlet apparatus, along with
the resin.

Absorbent
module

XAD-2
resin

The module with the resin was removed from the train, tightly sealed at
both ends and later transferred to the
soxhlet extractor.

Container 2

Probe and
cyclone

The probe and cyclone were washed

with a solution of methanol and methylene chloride, and the solution was
stored. The solution was concentrated
(at temperature less than 310.15K),
then it was added to the soxhlet apparatus along with the resin and filter.

Container 3

Probe and
cyclone

Both were also washed with toluene,

and the solution stored.

Sample was added 100:1 of internal

standard solution* to the solution,
then concentrated to a volume of about
3-5 mL (on a rotary evaporator with
temperature less than 310.15K); the
container 3 was rinsed 3 times with
toluene, and the rinse solution was
added to the rotary evaporator and
concentrated to near dryness. The
extraction was separately analyzed.

* isotopically labeled PCDD's and PCDF's at known concentrations under the heading "Internal Standards" in 10 mL of nonane.

Brazilian Journal of Chemical Engineering

Formation of Dioxins and Furans During Municipal Solid Waste Gasification

The gas chromatography operational conditions

are described in Table 4.
Table 4: Operational conditions during the chromatography and spectrometry analysis.
Parameters
Gas Chromatograph
Carrier gas
Oven

Conditions
Helium 1-1-2.10-8 m3.s-1
Initially at 423 K
Raised to 463 K and
then up to 573 K

High resolution mass spectrometer

Resolution
Ionization mode
Source Temperature

10000 m/e
Electron impact
523 K

Table 5: Analysis results of the solubilized extract

of ashes.
Determinated
compound
Aluminum
Barium
Chlorides
Phenol
Sulfate
Sodium

Results
(mg/L)
27.5
1.1
2734.0
0.04
262.0
1069.7

Total Equivalent Toxicity (TEQ) =

C
n =1

TEFn (1)

Toxicity Equivalence Factors (TEQF) established

by the local legislation, CONAMA Conselho Nacional do Meio Ambiente - resolution 316 (CONAMA,
2002), were employed; these factors agree with internationally accepted values established by NATO North Atlantic Treaty Organization (NATO, 1988).
RESULTS
Ash Characterization
The characterization analysis of the ash produced
in the gasification of MSW showed that the lixiviated
extract of ash presents concentrations of substances
indicated in Annex F of the NBR 10004 (ABNT,
2004a) that are below the established limits, so the ash
from the gasification process can be classified as nonhazardous waste. However, the solubilized extract
presented higher concentrations of some substances,
demonstrated in Table 5, which makes the ash a noninert waste, that must be properly disposed.
Dioxins and Furans
The dioxins and furans were sampled in the combustion gas flow. The conditions of the samplings are
presented in Table 6.

Maximum content in mg/L

in the solubilized extract
0.2
0.7
250.0
0.01
250.0
200.0

Table 6: Parameter during sampling of dioxins

and furans.
Parameter

Toxicity Equivalence Factors (TEQFs) have been

used to correlate the toxicity of various compounds
belonging to the group of dioxins and furans; the
most toxic compound in this class is 2,3,7,8-TCDD,
which has a TEQF equal 1. Therefore, each compound
must have its concentration multiplied by its respective equivalence factor. The sum of these final values
constitutes the total toxicity relative to 2,3,7,8-TCDD
(Equation (1)).

93

Sampling time
Gas flow rate normal dry basis
(mg.N-1m-3)
Gas flow rate
chimney conditions
(m3.h-1)
Gas temperature
(K)
Average isokinetic
(%)
Average gas velocity
(m.s-1)
Gas humidity
Content of carbon
dioxide (%)
Content of oxygen
(%)
Content of nitrogen
(%)

Sampling
mean
1
2
3
2h48min 2h48min 2h50min
2071
2078
2086
2078
7980

8146

8229

8118

872.15

881.15

105

104

104

104

5.76

5.88

5.94

5.86

8.61
11.6

9.28
9.00

9.91
10.2

9.27
10.3

3.40

5.00

3.00

3.80

85.0

86.0

86.8

85.9

880.15 877.82

The chromatographic assays conducted for three

samplings of municipal solid waste gasification in a
mobile grit gasifier furnished the mass of dioxins and
furans generated in each case. Application of the
TEQFs afforded the results depicted in Table 7.
The results in Table 7 revealed that the third sampling contained the largest mass of dioxins and furans. This was a consequence of alterations in operational conditions along gasification. System feeding
and combustion were controlled manually; the process was stable during the first two collection stages.
Changes that occurred during gasificationexcess
air present in the chamber during combustion and
variations in the amount of atmospheric air that entered the gasification chambermodified the process temperature. This culminated in different conditions over time, favoring dioxin and furan formation.
Higher pollutant generation during the process demonstrated that manual control caused instability.
Fortunately, it is easy to overcome this drawback by
automating the equipment operational controls:

Brazilian Journal of Chemical Engineering Vol. 32, No. 01, pp. 87 - 97, January - March, 2015

94

E. J. Lopes, L. A. Okamura and C. I. Yamamoto

combustion gas sensors can control excess air in the

combustion chamber; in the gasification chamber,
remote-controlled pressure and temperature sensors
can elicit a response that promptly equalizes the
process in terms of feedstock variations (the feedstock is MSW in this case). In other words, it is possible to optimize the process as indicated in the literature, so as to avoid the conditions that facilitate
dioxin and furan production. This control system is
applicable in plants that are not experimental or pilot,
which is the case of the plant of the present study.

Accounting for the volume employed during the

assay, one can obtain the emission of dioxin and furan
analogs, corrected with 7% oxygen (for comparison
with the limits established by the Emission Standards). Table 8 lists such data.
Even considering the third sampling, the dioxin
and furan emissions lay below the maximum value
allowed by the current legislation. The mean dioxin
and furan emission from the gasification in the mobile grit reactor was 0.28 ng N-1 m-3, expressed in
TEQ (Total Equivalent Toxicity), which lay below

Table 7: Mass of dioxins and furans obtained for samplings 1, 2, and 3.

Analytical result (in pg)
Dioxins and furans
2,3,7,8-TCDD (tetrachloro-dibenzo-p-dioxin)
1,2,3,7,8-PeCDD (pentachloro-dibenzo-p-dioxin)
1,2,3,4,7,8 HxCDD (hexachloro-dibenzo-p-dioxin)
1,2,3,6,7,8 HxCDD (hexachloro-dibenzo-p-dioxin)
1,2,3,7,8,9 HxCDD (hexachloro-dibenzo-p-dioxin)
1,2,3,4,6,7,8 HpCDD (heptachloro-dibenzo-p-dioxin)
OCDD (octachloro-dibenzo-p-dioxin)
2,3,7,8 TCDF (tetrachloro-dibenzofuran)
1,2,3,7,8 PeCDF (pentachloro-dibenzofuran)
2,3,4,7,8 PeCDF (pentachloro-dibenzofuran)
1,2,3,4,7,8 HxCDF (hexachloro-dibenzofuran)
1,2,3,6,7,8 HxCDF (hexachloro-dibenzofuran)
1,2,3,7,8,9 HxCDF (hexachloro-dibenzofuran)
2,3,4,6,7,8 HxCDF (hexachloro-dibenzofuran)
1,2,3,4,6,7,8 HpCDF (heptachloro-dibenzofuran)
1,2,3,4,7,8,9 HpCDF (heptachloro-dibenzofuran)
OCDF (octachloro-dibenzofuran)

1
73.00
42.10
4.42
2.33
2.57
1.70
0.24
69.80
35.61
281.35
56.09
60.13
5.11
35.28
8.08
1.50
0.38

Samplings
2
76.90
74.60
5.08
3.23
3.27
1.83
0.26
34.34
33.17
259.50
49.65
53.21
5.37
28.77
7.13
1.26
0.50

3
287.50
140.90
9.52
5.01
5.38
2.33
0.28
117.23
109.53
673.40
113.97
89.50
11.19
57.89
11.56
2.00
0.73

CI

145.80
85.87
6.34
3.52
3.74
1.95
0.26
73.79
59.44
404.75
73.24
67.61
7.22
40.65
8.92
1.59
0.54

122.73
50.35
2.77
1.36
1.46
0.33
0.02
41.59
43.40
232.91
35.42
19.27
3.44
15.28
2.33
0.38
0.18

145.80 138.88
85.87 56.98
6.34 3.14
3.52 1.54
3.74 1.66
1.95 0.38
0.26 0.02
73.79 47.06
59.44 49.11
404.75 263.56
73.24 40.08
67.61 21.80
7.22 3.89
40.65 17.29
8.92 2.64
1.59 0.43
0.54 0.20

x mean; - standard deviation; CI - Confidence Intervals

Table 8: Dioxin and furan emission for samplings 1, 2, and 3 corrected with 7% O2.
Analytical result (in ng N-1 m-3)

Dioxinas e furanos
2,3,7,8-TCDD (tetrahcloro-dibenzo-p-dioxin)
1,2,3,7,8-PeCDD (pentachloro-dibenzo-p-dioxin)
1,2,3,4,7,8 HxCDD (hexachloro-dibenzo-p-dioxin)
1,2,3,6,7,8 HxCDD (hexachloro-dibenzo-p-dioxin)
1,2,3,7,8,9 HxCDD (hexachloro-dibenzo-p-dioxin)
1,2,3,4,6,7,8 HpCDD (heptachloro-dibenzo-p-dioxin)
OCDD (octachloro-dibenzo-p-dioxin)
2,3,7,8 TCDF (tetrachloro-dibenzofuran)
1,2,3,7,8 PeCDF (pentachloro-dibenzofuran)
2,3,4,7,8 PeCDF (pentachloro-dibenzofuran)
1,2,3,4,7,8 HxCDF (hexachloro-dibenzofuran)
1,2,3,6,7,8 HxCDF (hexachloro-dibenzofuran)
1,2,3,7,8,9 HxCDF (hexachloro-dibenzofuran)
2,3,4,6,7,8 HxCDF (hexachloro-dibenzofuran)
1,2,3,4,6,7,8 HpCDF (heptachloro-dibenzofuran)
1,2,3,4,7,8,9 HpCDF (heptachloro-dibenzofuran)
OCDF (octachloro-dibenzofuran)
Total dioxins and furans (ng N-1 m-3)

1
0.0208
0.0120
0.0013
0.0006
0.0007
0.0005
0.0001
0.0199
0.0101
0.0802
0.0160
0.0171
0.0015
0.0101
0.0023
0.0004
0.0001
0.1938

Samplings
2
0.0241
0.0234
0.0016
0.0010
0.0010
0.0006
0.0001
0.0108
0.0104
0.0813
0.0156
0.0167
0.0017
0.0090
0.0022
0.0004
0.0002
0.1999

3
0.0804
0.0394
0.0027
0.0014
0.0015
0.0006
0.0001
0.0328
0.0306
0.1883
0.0318
0.0250
0.0031
0.0162
0.0032
0.0006
0.0002
0.4581

x mean; - standard deviation; CI - Confidence Intervals

Brazilian Journal of Chemical Engineering

CI

0.0418
0.0249
0.0018
0.0010
0.0011
0.0006
0.0001
0.0211
0.0171
0.1166
0.0211
0.0196
0.0021
0.0118
0.0026
0.0005
0.0002
0.2839

0.0335
0.0138
0.0007
0.0004
0.0004
0.0001
0.00001
0.0111
0.0118
0.0621
0.0093
0.0047
0.0009
0.0039
0.0006
0.0001
0.00005
0.1509

0.0418 0.0379
0.0249 0.0156
0.0012 0.0008
0.0010 0.0004
0.0011 0.0004
0.0005 0.0001
0.0001 0.00001
0.0211 0.0125
0.0171 0.0133
0.1166 0.0703
0.0211 0.0105
0.0196 0.0053
0.0021 0.0010
0.0118 0.0044
0.0026 0.0006
0.0005 0.0001
0.0002 0.00005
0.2839 0.1707

Formation of Dioxins and Furans During Municipal Solid Waste Gasification

the maximum value allowed by the Brazilian legislation (0.5 ng TEQ m-3) and the limits established in
other countries like the USA (0.1 to 0.3 ng TEQ m-3
for new plants and 0.3 to 0.8 ng TEQ m-3 for existing
plants), Canada (0.5 ng TEQ m-3), and Japan (0.1 to
0.5 ng TEQ m-3) (Caponi et al., 1998).
Incinerators working under controlled conditions,
in the absence of a gas treatment system, furnish
results above this value (Chang et al., 2009).
In incinerators with a simple gas cleaning system
consisting of only an electrostatic precipitator, Abad
et al. (2003) found levels between 44 and 111 ng
TEQ/m3 of PCDD/F. They also noticed that emissions of dioxins and furans decreased, around 15 ng
TEQ/m3, when a semi-dry scrubber began to operate,
but only with the installation of the fabric filter were
levels around 0.30.4 ng TEQ/m3 achieved (ABAD
et al., 2003).
Dioxin and furan emission after combustion of
the synthesis gas was low: the system probably did
not reach the conditions necessary for the de novo
synthesis to take place or for the precursors to form.
Gasification improves combustion conditions.
During the process, a fuel gas is formed prior to
combustion, elevating the temperature to 950-1050 C.
In this temperature range, the synthesis gas undergoes stable and complete combustion, avoiding the
generation of chlorinated precursors. The carbon
conversion rate is also higher, providing the ideal
conditions for fuel burning. This prevents the production of carbonized material; i.e., fixed carbon,
another precursor of dioxins and furans (Tanigaki et
al., 2012). This happens because the gasification
process occurs in distinct, individually controlled
stagesthe reactions that transform MSW into the
synthesis gas are not restricted to the same temperature conditions or the highly oxidizing incineration
environment.
The exhaust gases temperature also affects dioxin
and furan formation in the post-combustion region.
Maximum and minimum formation occurs around
350 C and outside the 200-450 C range, respectively.
Nevertheless, even if the optimal temperature conditions occur in the post-combustion region, the lack of
fly ash and fixed carbon in this stage diminishes
dioxin and furan production.
CONCLUSION
The mechanisms and models of dioxin and furan
formation described in the literature, as well as the
results of the analyses conducted in the gasifier, allowed us to verify that gasification followed by com-

95

bustion releases significantly less PCDDs and

PCDFs than the usual MSW incineration.
According to Suzuki et al. (2004), the presence of
molecular oxygen in the gas flow is essential to generate dioxin and furan; during the gasification process, an oxygen deficit must exist, so that the feedstock undergoes partial oxidation only, to produce
synthesis gas, which do not allow the formation of
dioxins and furans.
Chemicals like calcium oxide (CaO), sulfur, and
nitrogen compounds can also inhibit PCDD and
PCDF formation (Cheng and Hu, 2010). During
MSW gasification, it is likely that sulfur and nitrogen compounds arising from the organic matter present in the waste contribute to suppressing dioxin
and furan formation.
The gases were collected without any treatment;
that is, they were directly taken from the exhaust gas
outlet. Therefore, the implementation of simple gas
treatment systems can further reduce the values reported in this paper.
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