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Department of Chemical Engineering, University of Rome La Sapienza, Via Eudossiana 18, 00184 Rome, Italy
b
Department of Physics, University of Rome Roma Tre, Via della Vasca Navale 84, 00146 Rome, Italy
Received 7 December 2001; revised 6 March 2002; accepted 13 March 2002; available online 19 April 2002
Abstract
Solid waste, in dealing with the growing presence of organic compounds, especially plastics, can be considered an important source of
energy since they are inexpensive and easily obtainable materials. However, the presence of polyvinyl chloride (PVC) in the waste can result
in a recycling problem when thermal treatment is involved.
This work shows the possibilities of recovering energy from waste containing PVC by a gasication process without additional dechlorination facilities.
Experimental data obtained in a bench scale two-stage reactor indicate that the addition of Na2CO3 in a blend containing refuse-derived
fuel (RDF) and PVC is efcient in eliminating chlorine from the produced off-gas. On the contrary, the less expensive calcium compounds do
not show a satisfactory chlorine removal. A thermodynamic simulation of the process substantially leads to the same results.
Starting from this study, the working conditions for gasifying waste blends containing PVC in a scaled-up two-stage reactor can be
predicted. According to the simulation, the obtained syngas shows that the polluting compounds content is lower than the Italian law limit. As
a consequence, it can be used directly to obtain electric power and/or local heating. q 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Gasication; PVC; Gas dechlorination; Energy recovery
1. Introduction
The problem of disposal of municipal wastes due to
declining landll capacity, together with the increasing
cost of petroleum products, has encouraged research on
the possibility of their conversion into useful forms of
energy or chemical products. Solid waste, in fact, in dealing
with the growing presence of organic compounds, especially plastics, can be considered an important source of
energy since they are inexpensive and easily obtainable
materials. Among plastics, polyvinyl chloride (PVC) gives
an important contribution. PVC, in fact, due to its chemical
and mechanical characteristics, is widely used in building,
transport, packaging, electrical/electronic and healthcare
applications [1] and, with an annual world output of 19
millions tons, is second only to polyethylene for the
volumes of thermoplastic materials produced [2]. The
simplest and most effective method for recovering energy
from solid wastes is incineration. This process can utilise a
wide variety of materials, but the presence of PVC can result
in a recycling problem. PVC, in fact, due to its high chlorine
* Corresponding author. Tel.: 139-644-585566; fax: 139-644-585416.
E-mail address: fausto.pochetti@uniroma1.it (F. Pochetti).
q
Published rst on the web via Fuelrst.comhttp://www.fuelrst.com
0016-2361/02/$ - see front matter q 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0016-236 1(02)00097-2
1828
Table 1
Physical and chemical characteristics of the used RDF
Physical properties
Humidity
Volatile substance (dry basis)
Fixed carbon (dry basis)
Ash (dry basis)
Size
HHV
3.67% mass
73.06% mass
13.16% mass
13.78% mass
, 1 mm
17.50 MJ/kg
47.80
6.80
1.87
29.75
, 0.1
, 0.1
thermodynamic model useful for predicting the performance of a scaled-up two-stage gasication reactor.
2. Experimental
2.1. Materials
The RDF used in the gasication tests was supplied by
AMA (Municipal Environment Company of Rome). Prior to
use, the RDF was ground and mixed in order to obtain a
homogeneous mixture with a grain size suitable for feeding
the bench scale apparatus. The physical and chemical
characteristics of the used RDF were determined.
The physical properties measured included ash content,
humidity, volatile matter, xed carbon and the higher
heating value (HHV). The chemical analysis included the
determination of the elements C, H, N, O, S and Cl. The
results of these analyses are presented in Table 1. PVC high
molecular weight (MW approximately 200,000), supplied by
BDH, Na2CO3, CaO and Ca(OH)2, supplied by Aldrich,
were also used.
2.2. Apparatus and operative conditions
The gasication process, shown schematically in Fig. 1, is
1829
Cs 1CO2g ! 2CO
Cs 1H2 Og ! COg 1H2
COg 1H2 Og ! CO2g 1H2
Cn H2m 1 nH2 O ! nCO 1 m 1 nH2
Cn H2m 1 nCO2 ! 2nCO 1 2mH2
The working conditions of this stage are chosen in order to
support the reforming reactions of all hydrocarbons from
Table 2
Effect of oxygen injection and steam ow-rate on the off-gas characteristics
Run no.
500
160
0.035
74.66
8.87
10.98
5.49
0.80
11.15
50.6
500
70
0.060
75.85
10.12
5.19
8.84
1.13
12.64
31.1
500
160
0.065
76.37
10.12
6.31
7.20
1.32
12.11
19.6
500
70
0.115
75.75
9.68
5.91
8.66
1.23
12.51
25.5
500
160
0.116
74.62
10.81
6.02
8.56
1.27
12.49
16.8
500
160
0.149
74.66
8.87
10.98
5.49
1.42
10.59
11.05
1830
Table 3
Percentage of unreacted material in the residue as a function of stage one
temperature
T (8C)
Steam ow
rate (L(STP)/h)
Injected O2
(kgO2/kgRDF)
Unreacted material in
the residue (% mass)
500
500
600
600
700
700
160
160
160
160
160
160
0.035
0.116
0.035
0.116
0.035
0.116
50.6
16.8
13.7
4.5
4.2
0.2
Table 4
Comparison of typical gasication results
Working condition and
obtained results
Steam feed rate (L(STP)/h)
Injected oxygen/charge
ratio (kg/kg)
Stage one T (8C)
Stage two T (8C)
Unreacted materials in
residue (%)
H2 (%vol.)
CO (%vol.)
CO2 (%vol.)
CH4 (%vol.)
3
Heating value (MJ/m(STP)
)
Yield in dry gas (Nm 3/kg)
Tar dragged by the gas
RDF
RDF 1 PVC
160
0.116
160
0.116
160
0.116
600
1000
4.5 ^ 1
600
1000
28.5 ^ 3
600
1000
9.9 ^ 2
73.04
8.89
9.77
8.30
11.99
1.55
Absent
69.6
11.4
13.5
5.5
10.92
0.697
Absent
71.7
10.0
12.4
5.9
11.13
1.19
Absent
1831
Table 5
Alkaline compound efciency in chlorine removal during RDF 1 PVC gasication
PVC (mass %)
Reagent type
PVC/reagent ratio
Steam (L(STP)/h)
Feed Cl (g)
Cl in syngas (g)
Cl in ash (g)
10
10
10
10
10
10
10
10
10
10
10
20
CaO
CaO
Ca(OH)2
Ca(OH)2
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Stoichiometric
2 stoichiometric
Stoichiometric
2 stoichiometric
Stoichiometric
Stoichiometric
Stoichiometric
2 stoichiometric
1.2 stoichiometric
1.2 stoichiometric
1.2 stoichiometric
160
160
160
170
180
160
190
190
190
160
190
170
1.43
1.32
1.32
1.35
1.33
1.36
1.34
1.33
1.39
1.34
1.34
2.84
1.28
0.27
0.25
0.38
0.30
0.11
0.25
0.21
. 0.01
. 0.01
. 0.01
. 0.01
0.14
1.05
1.07
0.97
1.03
1.25
1.09
1.12
1.39
1.34
1.34
2.84
Table 6
Comparison between experimental data and thermodynamic predictions in a blend containing 10% of PVC
Dry gas composition
H2 (%vol.)
CO (%vol.)
CO2 (%vol.)
CH4 (%vol.)
3
Yield in dry gas m(STP)
/kg
Experimental
69.61
11.38
13.38
5.53
0.697
Thermodynamic predictions
Reforming and
water-shift reaction
Water-shift reaction
68.36
23.55
6.29
0.00
0.741
65.74
20.70
8.36
3.29
0.683
1832
Table 7
Comparison between experimental and calculated value of Chlorine
removal using sodium (1.2 times the stoichiometry) and calcium
compounds (2 times the stoichiometry)
Cl removal (%)
Na2CO3
CaO
Ca(OH)2
Experimental
Calculated
. 99.9
81.1
77.4
100
83
79
1833
6. Conclusions
Experimental data obtained with a bench scale two-stage
reactor indicate that Na2CO3 is efcient in eliminating chlorine evolving from blends consisting of RDF and PVC and
containing up to 20% of the latter. On the contrary, the less
expensive calcium compounds do not show a satisfactory
chlorine removal.
The data indicate also that stage one temperature, O2/
charge ratio and Na2CO3 addition act positively on the
amount of unburned char. Stage two temperature at