Fuel 130 (2014) 92–99

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Fuel
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Formation of PAHs during the pyrolysis of dry sewage sludge

Qianjin Dai a, Xuguang Jiang a,⇑, Yunfan Jiang b, Yuqi Jin a, Fei Wang a, Yong Chi a, Jianhua Yan a
a
State Key Laboratory of Clean Energy Utilization, Institute for Thermal Power Engineering, Zhejiang University, Hangzhou 310027, PR China
b
Department of Information Science and Electronic Engineering, Zhejiang University, Hangzhou 310027, PR China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 16 PAHs were numerously formed

during pyrolysis of dry sewage
sludge.
 Temperature, sample mass, residence
time and gas flow all had influences.
 PAHs yielded most at 950 °C while
TEQ was highest at 1150 °C.
 PAHs formation was favoured in fuel
rich condition.
 PAHs in different residence time of
2–16 s was highest at 10 s.

a r t i c l e i n f o a b s t r a c t

Article history: The formation of the 16 polycyclic-aromatic hydrocarbons (PAHs), characterized by USEPA as priority
Received 4 February 2014 pollutants, was studied during the pyrolysis of dry sewage sludge in a wide range of operation conditions,
Received in revised form 19 March 2014 i.e., reaction temperature (250–1250 °C), sample mass (0.1–4 g), gas residence time (2–16 s) and gas flow
Accepted 8 April 2014
(50–1000 mL/min). The pyrolysis was conducted in a tubular reactor with well-controlled temperature
Available online 20 April 2014
profile and carrier gas flow. The yield of PAHs strongly increased with temperature, reaching a maximum
value at 950 °C, while the toxicity equivalent (TEQ) became highest at 1150 °C. The sample mass also
Keywords:
influenced upon both the PAHs concentration and the TEQ, with the lowest output found for 1 g sample;
Sewage sludge
Pyrolysis
rising residence time of the gas flow inflates the PAHs formed and their TEQ up to 10 s, and then they
Temperature decreased slightly. Raising the gas flow from 50 to 100 mL/min moderately decreases the concentration
Sample mass of PAHs, yet sharp declines their TEQ. To evaluate any influences of the experimental parameters the
Gas residence time fractional distribution of the total PAH amount and the TEQ of the 16 PAHs, as well as their subtotal
grouped by ring number, were separately displayed. The present results may be valuable for assessing
sewage sludge pyrolysis as thermal treatment method and also for studying the formation and
destruction mechanism of PAHs during sludge pyrolysis.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction potential carcinogenic and mutagenic characteristics and harmful

Polycyclic aromatic hydrocarbons (PAHs) are a group of ubiqui-
tous organic contaminants drawing great public concern for their
⇑ Corresponding author. Tel.: +86 571 87952775; fax: +86 571 87952438.
E-mail address: jiangxg@zju.edu.cn (X. Jiang).
implication for human health [1,2], which become more serious
still in winter [3]. PAHs are also precursors of PM (particulate mat-
ter), formed in locally fuel rich areas [4] and a great issue in China.
The global distribution of PAHs is also influenced by the thermal
treatment of biomass and as chemically stable pollutants. PAHs
also accumulated in the atmosphere regardless of long-range

http://dx.doi.org/10.1016/j.fuel.2014.04.017
0016-2361/Ó 2014 Elsevier Ltd. All rights reserved.
 Q. Dai et al. / Fuel 130 (2014) 92–99
transport [5]. Thus PAHs emissions should be reduced to protect
the environment.
PAHs have been extensively studied in the pyrolysis of coal
[6–11], wood [12], wastes tires [13] and other biomass: gas [14],
tar [15], char [16] analysis and the formation mechanism of PAHs
have also been discussed in some detail [17,18]. Catechol [19],
propyne [20], and 1,3-butadiene [21] were also submitted to
pyrolysis separately or together to investigate PAHs emissions.
However, the formation of PAHs depends much on their source
and the reaction conditions [22]. PAHs emission is highly influ-
enced by the pyrolysis operating conditions (temperature in
pyrolysis of terpenes [23,24], acetylene [4], sample mass, gas
residence time, gas flow); however the subject is still causing some
controversy [4].
Sewage sludge is raising great concerns in China for its rapidly
increasing amount and concomitant risks for human health and
the environment [25]. Pyrolysis of sewage sludge shows great
advantage over combustion in terms of low cost in pollutant con-
trol [26,27]. Yet, the formation of PAHs during sewage sludge pyro-
lysis is of great concern [28].
In the pyrolysis of sewage sludge PAHs were usually discussed
but mostly for qualitative analysis [29] and general discussion
[15,22]. Some parameters, such as temperature, residence time
have been reviewed [30]. Other parameters such as sample mass,
gas residence time and gas flow are rarely discussed in literature.
In this study, the 16 PAHs, characterized by USEPA as priority
pollutants were analyzed in the gas effluent evolving during sew-
age sludge pyrolysis in a tubular reactor. The parameters, temper-
ature, sample mass, gas residence time and gas flow were all varied
to investigate their influence on PAHs emission. The formation and
destruction mechanism of PAHs are discussed. The results may also
be useful in designing sewage sludge disposal for energy recovery
and environmental protection.
2. Experimental
2.1. Reagents and materials
Sewage sludge was collected from the wastewater treatment
plant of Shi Dong Kou in Shanghai, China. The sludge underwent
aerobic digestion and mechanical dehydration before sampling.
The wet sewage sludge with moisture of 84.2 (wt.%) was dried in
a fluidized bed at 85 °C. The dry sewage sludge with moisture of
6.24% was then ground, sieved (80–200 mesh), and stored in
brown bottles. Proximate and ultimate analysis results on air dry
basis are presented in Table 1. The values of Mad, Aad, Vad and Fcad
were determined according to method GB/T212-2008 of China. The
elementary analysis of Cad and Had were determined by the Liebig
method (ISO 625-1996). The content of Nad was determined by the
semimicro Kjeldahl method (ISO 333-1996). The content of Sad was
determined by the IR spectrometry (ISO 19579-2006). The content
of Clad was determined by combustion-hydrolysis/ion chromatog-
raphy (IC) Method. The content of Oad was determined by
Table 1
Proximate and ultimate analysis of sewage sludge (mass%).
Mad Aad Vad Fcad
6.24 43.05 44.99 5.72
ad% = air dry basis.
M = moisture content.
A = ash content.
V = volatile matter content.
Fc = fixed carbon content.
C, H, N, S, O, Cl = the elements composing the combustible fraction.
Qb = net calorific value.
93
difference. Dichloromethane (DCM), hexane and copper powder
were obtained from ShanghaiHuShi Corporation.
2.2. Experimental study
All experiments were performed in a horizontal high tempera-
ture resistant (up to 1400 °C) quartz tubular reactor (diameter
20 mm, length 600 mm) (Fig. 1). The furnace was heated to the tar-
get temperature and then maintained at this temperature (±2 °C).
Approximately 1 g (±0.01 g) of dried sewage sludge was evenly
loaded into a quartz crucible (width 10 mm, length 100 mm) and
then the crucible was introduced into (the right side in Fig. 1) a
horizontal quartz reactor tube, at a temperature below 100 °C.
The gas outlet was connected to a set of sampling apparatus, com-
posed of a tube with XAD-2 resin and two bottles of DCM, after
purging the reactor for 10 min with nitrogen at a flow rate of
3 L/min to avoid potential impacts of oxygen. The flow rate of
nitrogen carrier gas is adjusted to 0.2 L/min, sufficient to prevent
the pyrolysis gas generated from accumulating in the tube and at
the same time not to affecting the temperature of the sample too
much. Then, with a quartz stick the crucible is pushed to the centre
of the reactor and pyrolysis starts. The generated gases passed
through the sampling apparatus, consisting of a XAD-2 resin
column and a set of DCM scrubbing solutions contained in ice
baths, to absorb PAHs and other non-condensed compounds from
in the gaseous effluent. After each pyrolysis run of 30 min the
furnace was turned off and the sample was allowed to cool in an
inert atmosphere for 30 min almost down to room temperature.
The residue was then weighted and saved. The resin and DCM were
saved and analyzed for PAHs.
Temperature was measured by a K type thermocouple and the
temperature distribution profile in the reactor at 850 °C (Fig. 1)
was shown to be representative. It was observed that a tempera-
ture close to set point is reached on the whole. Distance values
in Fig. 1 range from 50 to 350 mm, while the outlet point and
inlet point remain below 200 °C for all pyrolysis runs.
Pyrolysis runs with different temperature, ranging from 250 to
1250 °C, were conducted by adjusting the furnace temperature to
target temperature. The sample mass loaded was varied (mass of
0.1 g, 0.4 g, 1 g, 2 g, 4 g) to investigate the influence of sample
mass. The pyrolysis gas residence time was controlled between 2
and 16 s by adjusting the sample location from 2 to 16 cm
(Fig. 1), while the gas flow rate was calculated to 1.06 cm/s when
a flow of 200 mL/min nitrogen was induced. The gas flow rate
was adjusted from 50 to 1000 mL/min using a rotameter. The 24
test conditions are all listed in Table 2.
2.3. PAHs analysis
The EPA method 8100 was taken as reference, with slight mod-
ification in the PAHs analysis. Soxhlet extraction according to EPA
method 3540C was used as extraction procedure to guarantee good
contact between solid sample and solvent [31]. Some 2 g cleaned
Cad Had Nad Sad Oad Qbad (kJ/kg)
25.97 3.49 4.49 0.81 15.95 11 580
94 Q. Dai et al. / Fuel 130 (2014) 92–99

Fig. 1. Schematic view of the experimental set-up showing the axial temperature distribution for the experiment at 850 °C.

Table 2
Experimental conditions.

Run Variable Nominal temperature (°C) Sample mass (g) Gas residence time (s) Gas flow (mL/min)
P1 Temperature 250 1 10 200
P2 350
P3 450
P4 550
P5 650
P6 750
P7 850
P8 950
P9 1050
P10 1150
P11 1250
P12 Sample mass 850 0.1 10 200
P13 0.4
P14 2
P15 4
P16 Gas residence time 850 1 2 200
P17 4
P18 8
P19 12
P20 16
P21 Gas flow 850 1 10 50
P22 100
P23 400
P24 1000

copper powder was mixed with the sewage sludge before extrac-
tion to eliminate sulfur according to EPA method 3660B. Silica
gel clean-up was adopted according to EPA method 3630C while
rota-evaporation was used to concentrate the sample solution.
The 16 PAHs characterized by USEPA as priority pollutants were
determined using GC (Varian CP-3800, equipped with a 30 m *
0.25 mm * 0.25um DB-5MS capillary)/MS (1200 L) in a selected
ion monitoring mode (SIM). The carrier gas was He (1 mL/min)
while the injection mode was splitless (270 °C, 1 lL). The tempera-
ture program started at 50 °C, held for 1 min then the temperature
was raised to 300 °C at a rate of 20 °C/min and held there for 7 min.
The transfer line temperature was set at 300 °C and the Electron
impact (EI) source at 270 °C. The PAHs were determined using the
external standard method. A standard mixture of the 16 EPA-PAHs
was supplied by SIGMA–ALDRICH (PAHs concentration of
2000 lg/mL, and a solvent mixture of methylene chloride: benzene,
v:v = 1:1). The PAHs concentrations were calculated with a group
of 5 concentration levels ranging from 0.05 lg/mL to 1 lg/mL with
hexane as solvent. The GC/MS SIM profile programmed in the MS
and the concentration of external standards calculated using the
 Q. Dai et al. / Fuel 130 (2014) 92–99 95

Table 3
The working curve used to quantity PAHs with GC/MS.

PAHs TEF SIM MS window time (min) RT (min) 0.05 lg/mL 0.1 lg/mL 0.2 lg/mL 0.4 lg/mL 1 lg/mL Correlation coefficients Sewage sludge (mg/kg)
Nap 0.001 128 5–7 6.256 0.048 0.105 0.213 0.390 0.946 0.999390 0.0125
Acpy 0.001 152 7–8.5 8.141 0.049 0.104 0.209 0.389 0.970 0.999754 0.0025
Acp 0.001 154 8.353 0.049 0.104 0.209 0.385 0.978 0.999656 0.0130
Flu 0.001 166 8.5–9.5 8.985 0.049 0.103 0.209 0.387 0.979 0.999713 0.1640
Phe 0.001 178 9.5–11 10.168 0.049 0.104 0.211 0.388 0.964 0.999654 0.0040
Ant 0.01 178 10.231 0.049 0.105 0.208 0.378 0.994 0.999192 0.0045
Fla 0.001 202 11–12.5 11.623 0.049 0.103 0.212 0.385 0.972 0.999560 0.0055
Pyr 0.001 202 11.899 0.049 0.103 0.212 0.380 0.984 0.999298 ND
BaA 0.1 228 12.5–14 13.357 0.049 0.109 0.207 0.382 0.999 0.999293 0.009
CHR 0.01 228 13.401 0.048 0.103 0.198 0.406 0.945 0.999058 0.0090
BbF 0.1 252 14–16 14.840 0.049 0.103 0.213 0.373 0.996 0.998630 0.0090
BkF 0.1 252 14.886 0.049 0.104 0.207 0.384 0.987 0.999625 0.0095
BaP 1 252 15.392 0.049 0.105 0.207 0.380 0.991 0.999381 0.0010
IND 0.1 276 16–22 17.832 0.050 0.101 0.202 0.381 1.026 0.999008 ND
DBA 1 302 17.905 0.049 0.104 0.201 0.385 1.008 0.999533 0.0025
BghiP 0.01 276 18.544 0.049 0.102 0.205 0.380 1.014 0.999121 0.0050

working curve is given in Table 3. The linear fitting of the resultant
calibration curves shows good correlation coefficients between
0.9986 and 0.9997 for each compound.
The gas sample included XAD-2 resin and 250 mL DCM. The
XAD-2 resin was extracted using 250 mL DCM, and then concen-
trated to 1 mL to transform the solvent to hexane; after the
cleanup procedure, the sample was concentrated and fixed to
10 mL using hexane. Then 1 lL of the fixed sample was introduced
to GC/MS analysis. The detection limit during GC/MS analysis was
0.001 lg/mL for each of the 16 PAHs. Considering a sample mass of
1 g and the fixed solvent volume, the detection limit for the PAHs
yield was 0.01 mg PAHs per 1 kg dry sewage sludge. The original
content of PAHs was detected by using the same method with
XAD-2 resin: 20 g sewage sludge (dry basis) was extracted. The
results were listed in Table 3.
3. Results and discussion
The toxic equivalent factor (TEF) was defined in order to charac-
terize the carcinogenic properties of PAH more precisely, compar-
ing every compound with the BaP, which has the highest value of
TEF (Table 3) [32]. The carcinogenic equivalence (KE), referred to
as toxic equivalent (TEQ), is a parameter that determines the inha-
lative carcinogenic potential caused by airborne-PAH. It can be
determined using the TEF concept. These TEQ-values were also
determined in our work to evaluate the influence of different oper-
ation conditions on the harmful health effect of the gaseous effluent
of sewage sludge pyrolysis, and to characterize the real toxicity.
The 16 EPA-PAHs are classified into high molar weight (HMW)
PAHs with five and six rings (BbF, BkF, BaP, IND, DAB, BghiP),
middle molar weight (MMW) PAHs with four rings (Fla, Pyr, BaA,
CHR), and low molar weight (LMW) PAHs with two and three rings
(Nap, Acpy, Acp, Flu, Phe, Ant) [30].
Results were expressed as mg PAHs generated during the pyro-
lysis of 1 kg dry sewage sludge. The PAHs in the original sewage
sludge totaled 0.251 mg/kg, a rather low value for sewage sludge,
since it varied from 0.096 to 7.718 mg/kg for nine samples from
Tunisia [33]. The values of the PAHs generated in different condi-
tions are displayed in the supplementary material (Tables 4–7
and Figs. 6–17 classified according to ring number and PAHs distri-
bution profiles).
3.1. Influence of the temperature on total PAHs and ring number
Temperature is the most investigated parameter in PAHs forma-
tion. The sample mass, gas residence time and gas flow were
separately fixed to 1 g, 10 s and 200 mL/min when temperature
was varied from 250 °C to 1250 °C. PAHs yield first strongly
increased when temperature was raised while the total concentra-
tion peaked at 950 °C, and the total TEQ-value culminated at
1150 °C (Fig. 2).
At low pyrolysis temperatures of 250–550 °C, PAHs seem still to
be influenced by their original content (Table 3) in sludge, with
mainly Nap, Acp, Flu present. In our previous TG experiments
sewage sludge pyrolysis began at temperatures lower than
200 °C [34]. Thus PAHs began to be released already at 250 °C.
The decomposition of biodegradable materials, dead bacteria
and non-biodegradable polymers in temperature region of
170–500 °C all may contribute to the release of PAHs from the
sample already at temperature below 550 °C.
When the temperature surpassed 650 °C, PAHs yields increased
greatly, all along with the temperature rising to 850 °C, which is
consistent with other research of PAHs in pyrolysis, where PAHs
(mainly Nap, Flu, Phe, Fla, BghiP) increased with temperature rising
from 600 to 900 °C for polyethylene pyrolysis [35].
Between 850 °C and 950 °C, all PAHs but Acpy and Flu further
rose. The decline in Acpy and Flu was also observed in acetylene
pyrolysis [4] for relatively low temperature, which may indicated
that Acpy and Flu have relatively low stability.
When temperature raised further from 950 to 1050 °C, most
LMW PAHs (Nap, Flu, Phe, Ant) decreased, while most HMW PAHs
(BbF, BkF, BaP, IND, BghiP) amplified, still leading to a total drop.
This may be explained by the rupture of aromatic rings in LMW
PAHs above 950 °C [36]. As an alternative, HMW PAHs may also
be pyro-synthesized from lower rings [37] in the competition
between formation and destruction of PAHs, while HMW may be
easier to be synthesized than decomposed at this atmosphere of
high concentration of LMW, which promoted the chemical equilib-
rium to HMW PAHs synthesis more than rupture, regardless of
reaction acceleration caused by the temperature rise.
When the temperature augmented from 1050 °C to 1150 °C, all
PAHs but Acp, Flu, Pyr, BaP, IND decreased, continuing a total
diminution at rising temperature.
When temperature rose to 1250 °C, all PAH-species were head-
ing towards destruction.
From the above analysis, most PAHs show similar trends of
peaking at a specific temperature (except for Acpy, Flu); Nap,
Phe, Ant, BaA, CHR, DBA peaked at 950 °C, Fla, BbF, BkF, BghiP at
1050 °C, and Acp, Pyr, BaP, IND at 1150 °C. The difference of peak
temperature presumably represented their relative stability in
the complicated thermal reactions.
In the pyrolysis of polyvinyl chloride a high peak of PAHs (BaA,
BbF, BaP, DBA, Chr, BkF, INd) yield was at 850 °C [38]. In the
pyrolysis of polyphenolic compounds the LMW PAHs exhibited a
maximum at 870 °C [39]. In the pyrolysis of acetylene some light
96 Q. Dai et al. / Fuel 130 (2014) 92–99
Fig. 2. Influence of the temperature on total PAHs and their TEQ.
PAHs-priority (Nap, Flu, Ant, BaA, Acp) were diminished from
1073 K to 1473 K while there was a maximum for other heavier
PAHs at 1173 K, attributed to the competition between formation
and destruction reactions of PAH [40], the less reactive and porous
characteristic of soot particles formed at higher temperature also
leads to fewer PAHs adsorbed [41]. To sum up, the controversy
between different conclusions [4] induced may be due to their
different substances and atmospheres which to some degree
changed the stability of different PAHs, although they have the
same molecular structure.
When PAHs are classified by their ring number (Fig. 6), the
trend is clear in our work: the 2-ring and 3-ring PAHs peaked at
950 °C, the 4-ring and 5-ring PAHs peaked at 1050 °C, and the
6-ring PAHs peaked at 1150 °C. Thus it can be deduced that PAHs
with more rings are decomposed at higher temperature.
In the 16 PAHs distribution profile (Fig. 7), Flu dominated at
temperatures lower than 750 °C, which indicated that the same
formation mechanism prevails below 750 °C. The Nap faction
began to amplify greatly to attain nearly 30% at 850 °C and then
stay unchanged till 1300 °C. The fraction distribution is determined
by competitive reactions, as described above. It was observed that
Nap also dominated the PAHs in the pyrolysis of acetylene [40],
and of bio-fuel [42].
TEQ profile peaked at 1150 °C, although the concentration
culminated already at 950 °C. This is due to the LMW PAHs, with
low TEF, which were decomposed more than the HMW PAHs
with high TEF-value, when temperature rose from 950 °C to
1150 °C. The gain in TEQ between 850 °C and 950 °C in our
research (Fig. 2) was also observed in the pyrolysis of acetylene,
due to the formation of heavier PAHs with higher toxic potential
[40].
In the PAHs TEQ distribution profile (Fig. 8), Flu dominated TEQ
at temperatures lower than 650 °C, due to its high yield; BaP
greatly amplified its proportion at 850 °C and dominated at
1150 °C, leading to the high peak of total TEQ at 1150 °C. The turn-
ing point in the distribution profiles was 750 °C for both concentra-
tion and TEQ distribution (Figs. 7 and 8).
3.2. Influence of the sample mass on the total PAHs and ring number
distribution
The temperature, gas residence time and gas flow were sepa-
rately fixed to 850 °C, 10 s and 200 mL/min when sample mass
was inspected from 0.1 g to 4 g. When the sample mass increased
from 0.1 g to 1 g, the total PAHs and TEQ declined; however, when
the sample mass increased from 1 g to 4 g, PAHs augmented slightly
(Fig. 3). When the 16 PAHs are considered separately, they show
different trends. When the sample mass was raised from 0.1 g to
4 g Nap, Phe, Fla, BaA, CHR, BbF all declined, and only Flu and IND
amplified; moreover, Acpy, Acp and Ant peaked at 1 g, Pyr and
BkF peaked at 0.4 g, whereas BaP and DBA were lowest at 1 g. When
the influence of sample mass on PAHs yield was considered, higher
yield at less sample mass was observed by comparing different
operating conditions conducted by former researchers, while gas
effluent during coal pyrolysis yielded around 100 mg/kg PAHs at
0.5 g sample mass [6] comparing to around 1000 mg/kg PAHs at
0.001 g sample mass [7] ignoring their different apparatus.
The sample mass represents the concentration of fuel, which
can lead to extent variation of the pyrolysis reactions. Less fuel
led to more contact between the pyrolysis products and the nitro-
gen flow, therefore more complete pyrolysis of heavier molecule to
light hydrocarbon including the 16 PAHs, Nap being the most
prominent. However the obvious growth of Flu, when sample mass
increased, may indicate that Flu tends to form at fuel rich
atmosphere, where primary pyrolysis rather than secondary
pyrolysis was favored. It was confirmed when domination of Flu
at low temperature (Fig. 7) was considered. It was noted that Ant
was proliferated at 1 g.
When PAHs are classified by their ring number (Fig. 9), 2-ring,
4-ring, 5-ring were diminished while 3-ring 6-ring PAHs grew when
the sample mass increased due to Flu and IND’s special behavior.
From 16 PAHs distribution profile (Fig. 10), Nap, Flu and Phe
dominated (80%) the concentration at different mass sample, while
Nap decreased and Flu increased when the sample mass was raised
from 0.1 g to 4 g.
 Q. Dai et al. / Fuel 130 (2014) 92–99 97

Fig. 3. Influence of the sample mass on total PAHs and their TEQ at 850 °C.

When the TEQ distribution is considered (Fig. 11), BaP, Fla and
DBA yield most but not dominant.
3.3. Influence of the gas residence time on total PAHs and ring number
The temperature, sample mass and gas flow were separately
fixed to 850 °C, 1 g and 200 mL/min when gas residence time
was inspected from 2 s to 16 s. Residence time may be a very
important issue, largely determining the conversion of small
hydrocarbons into PAHs [4]. Amplified residence time of pyrolysis
vapors in the hot zone of the reactor will promote secondary reac-
tions including PAHs formation [43].
When the residence time grew from 2 s to 16 s, the amount of
PAHs rose until 10 s and then declined slightly (Fig. 4). This is con-
sistent with the observation that PAHs rose as the residence time
grew from 1.5 to 3.5 s at 1123 K and 1173 K in acetylene pyrolysis
[4]. In our study, 10 s may be a turning point at 850 °C, where
destruction of PAHs exceeds formation of PAHs. All of 16 PAHs,
except for Acy and BghiP peaked at 10 s, while Acy peaked at
12 s and BghiP was not detected. Thus the conclusion of all 16
PAHs peaking at around 10 s may be deduced at 850 °C. However
the trend would differ at different temperature [4].
When PAHs are classified by their ring number (Fig. 12), all
PAHs peaked at 10 s. The 3-ring PAHs are prominent, for their high
quantity. It is noted that Ant proliferated at 10 s.

Fig. 4. Influence of the gas residence time on total PAHs and their TEQ at 850 °C.
98 Q. Dai et al. / Fuel 130 (2014) 92–99
Fig. 5. Influence of the gas flow on total PAHs and their TEQ at 850 °C.
In the 16 PAHs distribution profile (Fig. 13), Nap, Flu and Phe
dominated (80%) the concentration at different residence time,
while the profiles tendency are not clear.
When the TEQ distribution is considered (Fig. 14), BaP, Fla and
DBA yield most but not dominant.
3.4. Influence of the gas flow on total PAHs and ring number
The temperature, sample mass and gas residence time were
separately fixed to 850 °C, 1 g and 10 s when gas flow was
inspected from 50 mL/min to 1000 mL/min. Gas flow changes the
residence time and also the gas phase concentrations. In our study
a gas flow of 50, 100, 200, 400, 1000 mL/min corresponds with a
residence time of 37.7 s, 18.8 s, 9.4 s, 4.7 s, 1.9 s separately.
When the gas flow was raised from 50 to 100 mL/min, the
residence time dropped and fuel concentration also reduced by a
factor 2. The resulting PAHs amounts decreased by 22.17% while
their TEQ dwindled by 74.77%. The sharp decrease was strongest
for high ring-number PAHs of DBA, BaP, which have a high TEF of
1. This shows that a long residence time combined with high con-
centration of fuel can lead to the synthesis of high TEF PAHs. While
longer residence time (over 10 s) leads to slightly lessening of BaP
and DBA (Table 6), high concentration appears to promote their
formation: BaP and DBA augmented, when sample mass was raised
from 1 g to 4 g (Fig. 5). Particularly BghiP was only detected at
50 mL/min. However, most of the other PAHs diminished due to
the drop in residence time, for decreasing fuel concentration from
4 g to1 g leads to their increase.
When the gas flow rose from 100 to 1000 mL/min, the residence
time dropped from 18.8 s to 1.9 s and the fuel concentration fur-
ther reduced, by one order of magnitude. The total PAHs and their
TEQ show a slight decline. Most PAHs (Nap, Acpy, Acp, Phe, Fla, Pyr,
BaA, CHR, BbF, BaP, IND, BDA) decreased due to the lower gas
residence time since they had trend of increase when fuel concen-
tration was reduced from 4 g to1 g (Fig. 3). Flu was special since it
shows a rising trend when the gas flow was raised.
It can also be concluded that the trends of PAHs for sample
mass and flow gas are roughly opposite, just like for combustion
conditions the air–fuel ratio is import for PAHs formation.
When PAHs are classified by their ring number (Fig. 15), all ring
PAHs have a descending trend when the gas flow was raised from
50 to 1000 mL/min, except for the 3-ring PAHs, due to the special
behavior of Flu.
The Nap, Flu and Phe dominated (80%) the 16 PAHs distribution
profile at different gas flow, except for 50 mL/min, where largely
high ring PAHs are formed (Fig. 16).
When the TEQ distribution is considered (Fig. 17), BaP, Fla and
DBA yield most however not dominant.
4. Conclusions
In the investigation into the influence of the operating condi-
tions, such as reaction temperature, sample mass, gas residence
time and gas flow, yield of most PAHs had similar trend according
to different conditions. When temperature was raised, PAHs
increased extensively at 850 °C and decreased considerably at
1250 °C. PAHs yielded most at 950 °C while TEQ was highest at
1150 °C. The trend was an integration of different formation and
destruction temperature of PAHs different ring.
When sample mass was raised from 0.1 g to 4 g, PAHs yields
decreased from 1288.00 mg/kg(0.1 g) to 868.22 mg/kg(1 g) and
then increased slightly due to the special growth of Flu. Flu tended
to be formed at fuel rich atmosphere, where primary pyrolysis
rather than secondary pyrolysis was favored.
When residence time of gas flow was raised from 2 s to 16 s,
PAHs and their TEQ increased before 10 s, and then decreased
slightly. 10 s may be a special residence time for reactions to
destroy PAHs molecular in sewage sludge pyrolysis.
The rise of gas flow from 50 to 100 mL/min led to moderate
decrease of concentration and sharp decrease of TEQ while
increase from 100 to 1000 mL/min led to slight fluctuation. The
extremely high TEQ for 50 mL/min was due to formation of PAHs
with 5-ring and 6-ring. The trend of PAHs for sample mass and flow
gas are roughly reverse, for they were together related to the air–
fuel ratio.
When the comprehensive comparisons of these parameters were
considered, Temperature obviously has the most influence while
sample mass may has the least influence on the PAHs formation.
 Q. Dai et al. / Fuel 130 (2014) 92–99
The relative influence orders of these parameters may be tempera-
ture, gas residence time, gas flow and sample mass while gas flow
reflected the integration of gas residence time and sample mass.
The results may be useful for pollutant control over sewage sludge
pyrolysis process. PAHs formation mechanism can be developed
from our following work.
Acknowledgments
Financial supports by the National Basic Research Program of
China (Grant No. 2011CB201500), the National High Technology
Research and Development Program (863 Program) of China (Grant
No. 2012AA063505), the Special Fund for National Environmental
Protection Public Welfare Program (Grant No. 201209023-4), the
Program of Introducing Talents of Discipline to University (Grant
No. B08026) and the National Key Technology Research and Devel-
opment Program of China (Grant No. 2012BAB09B01) are
acknowledged.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.fuel.2014.04.017.
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