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1 s2.0 S0956053X12000906 Main PDF
1 s2.0 S0956053X12000906 Main PDF
Waste Management
journal homepage: www.elsevier.com/locate/wasman
State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, China
Institute for Biodiversity and Ecosystem Dynamics, University of Amsterdam, Amsterdam, The Netherlands
a r t i c l e
i n f o
Article history:
Received 22 September 2011
Accepted 8 March 2012
Available online 3 April 2012
Keywords:
Sludge
Dioxins
Suppression
Hospital waste incineration
a b s t r a c t
Nitrogen containing compounds such as ammonia, urea and amines can effectively inhibit the formation
of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Sewage sludge accumulates both
sulfur and nitrogen during wastewater treatment so it could be used to reduce PCDD/Fs formation.
Indeed, it is observed in this study that the gas evolving from the sludge drying process can signicantly
suppress chlorobenzene (CBz) and PCDD/Fs formation from y ash collected from a hospital waste incinerator. For instance, the reduction of hexachlorobenzene (HxCBz) and PCDD/Fs amount was 92.1% and
78.7%, respectively, when the drying gas evolving from 2 g sludge ew through 2 g y ash. These tests
were conducted in the frame of projects devoted to hospital waste incineration. The disposal technology
for hospital waste (HW), developed in this institute, features rotary kiln pyrolysis combined with postcombustion followed by ue gas cleaning. Hence, some preliminary tests were devoted to investigate
dioxins suppression by co-pyrolysis and co-combustion of polyvinyl chloride (PVC) and sludge in lab
scale. More experimental research will be conducted to appropriately assess these effects of sludge on
PCDD/Fs emissions during co-pyrolysis/combustion of HW and sludge.
2012 Elsevier Ltd. All rights reserved.
1. Introduction
Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated
dibenzofurans (PCDFs) and hexachlorobenzene (HxCBz) are persistent organic pollutants (POP) which can induce various adverse
health effects. The Stockholm Convention denes the need to eliminate POP production and emissions. Waste incineration contributes the largest release of PCDD/Fs so a lot of studies focus on
dioxins emission control from waste incineration. Nitrogen containing compounds including ammonia, urea, amines and amine
salts (Kuzuhara et al., 2005; Samaras et al., 2000; Takacs and
Moilanen, 1991) have been proved capable of inhibiting dioxins
formation. Ruokojrvi et al. (2001) even found 91% reduction of total PCDD/Fs by adding 1 wt.% of urea to refuse derived fuel (RDF).
Sewage sludge is the excess cell material produced during biological wastewater treatment. It is high in nitrogen and sulfur
(Witter and Lopez, 1988); the average content of nitrogen in dry
sludge is approximately 4% (Francisca et al., 2005; Werther and
Ogada, 1999). Common disposal methods of sludge are landll
and incineration. Yet sludge dewatering and possibly drying are
essential for both methods (Gruter et al., 1990). Ammonia will be
desorbed during sludge drying, together with other volatile compounds (Deng et al., 2009a). However, heavy metals in sludge, such
Corresponding author. Tel.: +86 571 8795 2037; fax: +86 571 8795 2438.
E-mail address: lixd@zju.edu.cn (X. Li).
0956-053X/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.wasman.2012.03.007
1454
Fe
Cu
Zn
Hg
Ni
Cr
Pb
Se
As
Cd
13280.7
853.4
465.1
101.3
66.5
60.9
53.6
25.6
18.7
5.9
Table 1
Proximate and ultimate analysis of sludge (%, w/w).
105 C (6 h)b
200 C (1 h)c
a
b
c
Ma
Fc
Qb (J/g)
St
2.06
0.04
51.04
56.14
40.25
33.76
6.65
10.06
10,981
10,539
25.61
24.98
3.87
3.05
3.94
3.65
1.06
0.98
12.42
11.16
M, Moisture; A, Ash; V, Volatile; Fc, Fix carbon; Qb, Bomb caloric value; C, Carbon; H, Hydrogen; N, Nitrogen; St, Total sulfur content; O, Oxygen.
The raw sludge was heated at 105 C for 6 h, named as dried sludge (DS).
Residual sludge after the drying experiment of DS (200 C for 1 h).
1455
Reagents
A-1
A-2
A-3
A-4
A-5
/
/
2g
2g
2g
2g
2g
/
/
ash
ash + 2 g
ash + 4 g
ash + 2 g
ash + 4 g
RS
RS
DS
DS
Detection
No.
Reagents
Detection
CBz
CBz
CBz
CBz
CBz
/
/
B-1
B-2
B-3
C-1b
C-2
D-1c
D-2
2g
2g
2g
1g
1g
1g
1g
ash
ash + 1 g DS
ash + 2 g DS
PVC + 3% CuO
PVC + 3% CuO + 3% DS
PVC + 3% CuO
PVC + 3% CuO + 3% DS
A and B series experiments conducted in the tubular furnace (Fig. 1), C and D series experiments in the quadruple furnace (Fig. 2).
C series experiments belong to the series experiments of co-pyrolysis.
D series experiments belong to the series experiments of co-combustion.
106 C, held for 0.5 min; increased at 8 C/min to 250 C and held
for 15 min. The clean up procedure of PCDD/Fs samples was
according to the USEPA1613 method (U.S. EPA, 1994). High-resolution gas chromatography was performed with a high-resolution
mass spectrometer (HRGC/HRMS) (JEOL JMS-800D) and a DB5MS column (60 m 0.25 mm 0.25 lm) was applied for PCDD/
Fs analysis. The temperature program for the GC oven was set as:
initial temperature was 150 C, held for 1 min; increased at
25 C/min to 190 C; then increased at 3 C/min to 280 C; held
for 20 min. Target compounds were Tetra- to Octa- CDD/Fs (136
isomers). Details of the cleanup procedure and analysis method
of PCDD/Fs and CBz could be found in our previous study (Yan
et al., 2010).
reduced. For instance, the suppression percentage for each congener was 78.0% (TeCBz), 93.72% (PeCBz) and 92.01% (HxCBz) in A-4,
compared to A-1. HxCBz is a persistent organic pollutant, so its
emission control from waste incineration must be of concern too.
Considering the experimental result, sludge drying gas could be
used in HxCBz emission control. Chlorobenzenes are thought as
2000
(a)
1600
CO
NO
NH3
CO
1200
NO
800
ppm
a
b
No.
N2O
400
300
HCl
HCN
NH3
200
N2O
HCl
100
0
0
1000
HCN
2000
3000
Time, s
ppm
2500
(b)
2000
NH3
NH3
CO
NO
HCN
N2O
CO
1500
HCl
NO
300
HCN
N2O
200
100
0
0 HCl
1000
2000
3000
Time, s
Fig. 3. Emission of common gas pollutant in B series experiments (B-1 and B-3).
Table 4
Maximum values (ppm) for various gases and the reached time (s).
Compound
CO, ppm
NH3, ppm
HCN, ppm
CO, s
NH3, s
HCN, s
B-1
B-3
B-1a
B-3a
1961
1648
207
314
282
2524
79
543
32
209
9
55
460
460
/
/
525
545
/
/
500
540
/
/
A-1
A-4
A-5
40
150
B-1
B-2
B-3
120
90
60
30
20
O8CDF
H7CDF
H6CDF
T4CDF
P5CDF
O8CDD
H7CDD
H6CDD
P5CDD
T4CDD
10
O8CDF
H7CDF
H6CDF
HxCBz
P5CDF
PCBz
T4CDF
TeCBz
O8CDD
20
0
Yield, ng/g
60
H7CDD
(b)
B-2
B-3
80
H6CDD
1200
900
600
300
80
40
0
100
A-1
A-2
A-3
P5CDD
(a)
Inhibition,%
1600
1200
800
400
80
40
0
T4CDD
Yield, ng/g
Yield, ng/g
1456
Table 5
Experimental result: dioxins during co-combustion in C and D experiments.
C-1
C-2
D-1
D-2
PCDD/Fs, ng/g
I-TEQ, ng/g
Chlorination degree
828 63
1570 143
2850 159
2784 388
6.3 0.48
9.6 1.54
31.5 0.91
24.5 2.7
7.50
7.62
7.15
7.33
1457
(b) Sludge
100
0.0
DTG
40
Hydrocarbon
-1.0
20
80
TG, %
-0.5
DTG, %/T
TG, %
TG
60
-0.1
70
60
-0.2
VOC
50
-0.3
TG
DTG
40
-1.5
HCl
0.0
90
80
Fix carbon
30
0
200
400
600
800
1000
DTG, %/T
(a) PVC
100
200
400
T, C
600
800
-0.4
1000
T, C
Fig. 7. Thermogravimetric analysis (TGA) of PVC pyrolysis (Zhu et al., 2008) and sludge combustion (Jiang et al., 2010) (heating rate of 30 C/min) (TG, Thermogravimetric;
DTG, Differential Thermogravimetric).
(b)
(a)
60
C-1
C-2
D-1
D-2
40
Fraction, %
50
40
30
20
10
30
20
10
2
2
0
O8CDF
H7CDF
P5CDF
H6CDF
T4CDF
O8CDD
H7CDD
H6CDD
P5CDD
H7CDF
O8CDF
H6CDF
P5CDF
T4CDF
O8CDD
H7CDD
H6CDD
T4CDD
P5CDD
0
T4CDD
Fraction, %
50
the metal in sludge acted as the chlorination catalyst (Table 2). The
homolog pattern of PCDD/Fs is shown in Fig. 8. Highly chlorinated
species, especially O8CDF and H7CDF, predominated in PCDD/Fs.
Since the chlorine content of rigid PVC was over 50% and there
was active catalyst of CuO (3%). PCDFs formation was more favored
over PCDDs formation with the ratio of PCDFs to PCDDs being over
5.0 in all experiments.
4. Conclusions
In these experiments, two pieces of valuable information have
been observed as follows:
1. Sludge drying produced a high content of NH3 and HCN. These
nitrogen containing compounds could be used to effectively
suppress the formation of chlorinated organic pollutants
including HxCBz and PCDD/Fs. Also, a lower concentration of
NO was detected after the spray of the sludge drying gas.
2. Co-combustion/pyrolysis of PVC and dry sludge did not completely work as initially predicted. Hence co-pyrolysis/combustion of HW and sludge should be further investigated in lab
scale and real scale furnace.
Acknowledgements
This study was nancially supported by Major State Basic
Research Development Program of China (973 Program) (No.
2011CB201500) and Scholarship Award for Excellent Doctoral
Student granted by Chinese Ministry ofEducation. The authors convey our grateful acknowledgement to Dr. Amrita Pal for her help in
revising the text of this paper (amritapal2@gmail.com, Columbia
University, New York City, NY).
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