Академический Документы
Профессиональный Документы
Культура Документы
Waste Management
journal homepage: www.elsevier.com/locate/wasman
a r t i c l e
i n f o
Article history:
Received 24 July 2014
Accepted 13 October 2014
Available online 6 November 2014
Keywords:
Waste incineration
Zn recovery
Resource evaluation
Resource classication
a b s t r a c t
Solid residues generated at European Waste to Energy plants contain altogether about 69,000 t/a of Zn, of
which more than 50% accumulates in air pollution control residues, mainly boiler and lter ashes. Intensive research activities aiming at Zn recovery from such residues recently resulted in a technical scale Zn
recovery plant at a Swiss waste incinerator. By acidic leaching and subsequent electrolysis this technology (FLUREC) allows generating metallic Zn of purity > 99.9%. In the present paper the economic viability
of the FLUREC technology with respect to Zn recovery from different solid residues of waste incineration
has been investigated and subsequently been categorised according to the mineral resource classication
scheme of McKelvey. The results of the analysis demonstrate that recovery costs for Zn are highly dependent on the costs for current y ash disposal (e.g. cost for subsurface landlling). Assuming current disposal practice costs of 220 /ton y ash, resulting recovery costs for Zn are generally higher than its
current market price of 1.6 /kg Zn. With respect to the resource classication this outcome indicates that
none of the identied Zn resources present in incineration residues can be economically extracted and
thus cannot be classied as a reserve. Only for about 4800 t/a of Zn an extraction would be marginally
economic, meaning that recovery costs are only slightly (less than 20%) higher than the current market
price for Zn. For the remaining Zn resources production costs are between 1.5 and 4 times (7900 t/a Zn)
and 1080 times (55,300 t/a Zn) higher than the current market value. The economic potential for Zn
recovery from waste incineration residues is highest for lter ashes generated at grate incinerators
equipped with wet air pollution control.
2014 Elsevier Ltd. All rights reserved.
1. Introduction
In 2011 about 23% of Municipal Solid Waste (MSW) generated
within the European Union has been thermally valorised
(Eurostat, 2014), which amounts, together with commercial waste,
to about 78 million tons of total waste fed to Waste to Energy (WtE)
plants (CEWEP, 2011). Besides the production of electricity and
heat, MSW incineration (MSWI) goes along with the generation of
bottom ash and air pollution control (APC) residues, namely y
ashes (including boiler ash and lter ash) and lter cake. While in
many countries bottom ash is already processed in order to recover
some of the metals contained (mainly iron scrap, but also aluminium and copper), APC residues (which amount in total to about
2 million tons in the European Union) have been hardly considered
for resource recovery so far. In all European countries they are clas-
Corresponding author.
http://dx.doi.org/10.1016/j.wasman.2014.10.010
0956-053X/ 2014 Elsevier Ltd. All rights reserved.
sied as hazardous waste, which results from environmental concerns regarding the leachability of easily soluble salts (such as Cl,
Na or K) and heavy metals (such as Cd, Pb, Cu or Zn) on the one
hand, as well as the total content of As, Cd, Hg, and dioxins on the
other hand.
Due to these characteristics most APC residues are either landlled at hazardous waste landlls (this includes also the backlling
of former salt mines) or are stabilized with cement or other chemicals in order to comply with regulatory limit values for waste acceptance at non-hazardous landlls. Both practices are associated with
signicant costs, ranging between 200 and 250/t y ash (Astrup,
2008) and the loss of valuable materials (e.g. metals). Contrary to
that, only a small portion of APC residues, mainly from uidized bed
incineration, can be landlled in non-hazardous landlls without
prior treatment.
Only in few European countries attempts are made to recycle APC
residues (Astrup, 2008) or at least parts of them. In the Netherlands,
for instance, y ashes partly substitute ller material in asphalt
96
estimate on the associated costs can be given (3). The latter forms
the base for the subsequent classication of the different types of
ows and stocks of interest (4).
Due to the fact that investigations have a priori been dedicated
to the MSWI residues annually generated, the initial step of
resource prospection (step 1) has been left out in the frame of
the present investigations. Furthermore, contrary to the evaluation
of Lederer et al. (2014), only ow resources have been considered.
Flow resources are characterized by a continuous availability at
different intervals and are in case of natural resources also classied as renewable resources, which are in contrast to non-renewable stock resources. According to Lederer et al. (2014) wastes
generated can be considered as anthropogenic ow resources.
As for the present case study these ow resources are partly
classied as hazardous waste, costs associated with the conventional disposal of these waste have to be accounted for as revenues
when accomplishing the economic analysis of the recovery technology chosen.
2.1. Exploration of Zn ows in MSWI residues
In order to explore residues from waste incineration as
potential secondary resource for Zn, a detailed literature analysis
focusing on the following issues has been conducted:
The amounts of waste incinerated in European WtE plants
(CEWEP, 2011),
the technology of incineration applied distinguishing between
grate incineration & rotary kilns on the one hand and uidized
bed incinerators on the other hand (ISWA, 2006a, 2013), as they
determine the specic amount of different MSWI residues and
their respective content of valuable metals,
the technology of air pollution control (APC) systems (wet, dry
& semi-dry residue systems) used at European Waste-to-Energy
plants and the respective amount of APC residues (ISWA, 2013,
2006a), both again inuencing the content of valuable metals
(e.g. Zn) in APC residues,
the Zn content in different MSWI residues (e.g., Auer et al.,
1995; Hjelmar, 1996; Jakob et al., 1996; Abe et al., 2000;
Nagib and Inoue, 2000; Mangialardi, 2003; Aubert et al., 2004;
Hallgren and Strmberg, 2004; Ferreira et al., 2005; Aubert
et al., 2007; Van Gerven et al., 2007; Chiang et al., 2008;
Quina et al., 2008; Bontempi et al., 2010; Karlfeldt Fedje et al.,
2010b; Karlsson et al., 2010; Lam et al., 2010; Schlumberger,
2010; De Boom et al., 2011; Nowak et al., 2013; Boesch et al.,
2014), and
transfer coefcients describing the portioning of Zn to the different outputs of incineration plants (e.g., Schachermayer et al.,
1996; Brunner and Mnch, 1986; Morf and Brunner, 1998).
In all parameters of interest numerous data sources (as indicated above) have been utilized, which resulted in particular for
the Zn content in MSWI residues as well as for the transfer coefcients of Zn rather in ranges of values than in exact gures. The
deviations observed between the different sources have been
accounted for by using uncertainty ranges for the respective
parameters in the frame of the subsequent material ow and economic analyses.
Based on the results of the literature survey a material ow
model describing the ows of Zn through European WtE plants
has been established.
2.2. Economic Evaluation of Zn ows
The MFA model together with detailed information about the
recovery technology, its consumables and costs for alternative
97
Fig. 1. Procedure for the evaluation of anthropogenic resources (after Lederer et al., 2014).
disposal of MSWI residues, form the basis for the economic evaluation of Zn recovery. To the knowledge of the authors the only technology for recovering Zn from MSWI residues operating at large
scale is the FLUREC process, although other technologies (e.g.
Karlfeldt Fedje et al., 2014) for zinc extraction (producing a metal
concentrate of lower purity) have been developed in the recent
years. Therefore, the FLUREC technology has been assumed for
the economic evaluation of Zn resources present in MSWI residues.
Fig. 2 gives an overview of the FLUREC technology and summarizes the required operating supplies. Detailed information about
the specic quantities of the latter together with data about products and by-products are of major importance for the economic
evaluation. Boesch et al. (2014) who performed a LCA on waste
incineration enhanced with new technologies for metal recovery,
Fig. 2. Schematic process diagram of the FLUREC technology (acidic y ash leaching with integrated Zn recovery, whereby Zn powder is to be added for the reductive
separation of Pb, Cu, Cd during solidication) based on Boesch et al. (2014).
98
j1
C CP C FLUREC
Pn
cZn
i1 mOPi
pOPi
1
Pl
j1 mDPj
3. Results
3.1. Exploration of Zn ows in MSWI residues
n
l
X
X
mOPi pOPi
mDPj C DPj C INV mZn pZn mCon pCon
i1
(pZn < cZn < 10 pZn). Resource ows whose production costs are
above the threshold (of 10 times the market price) are counted
as other occurrences.
The classication according to the certainty of the existence of a
resource ow is structured as identied demonstrated, identied
inferred, and potentially undiscovered. To perform this classication,
the uncertainties determined for each Zn ow in the residues of
MSWI are used. Identied demonstrated resources are of proven
existence and knowledge is highly certain (condence that the
actual ow of Zn is at least this size is 90%). Identied inferred
resources are dened here as the amount of Zn ows between the
lower uncertainty bound (condence 90%) and the mean value of
the ow. The same amount of the material (due to symmetric
uncertainty ranges) is designated as potentially undiscovered
resources, which may exist but are highly uncertain. Finally, a
cross-classication is accomplished considering both, economic
viability and knowledge. Therein, reserves are resources that are
both identied demonstrated and economically extractable.
The reserve base further includes the part that is identied demonstrated and not protably extractable with current technology
and market conditions (classied as marginally economic).
mOPi is the specic mass of operating supply i (kg/t y ash) and specic energy demand (kW h/t y ash), mDPi is specic mass of residue
j (resulting from the FLUREC process) to be disposed of (kg/t y ash),
mZn is specic mass of metallic Zn recovered (kg Zn/t y ash), mCon
is specic mass of concentrate containing Pb, Cu and Cd (kg Zn/t y
ash), pOPi is market price for operating supply i and energy demand i
(/kg operating supply) or (/kW h), pZn is market price for metallic
Zn (/kg Zn), pCon is market price for concentrate containing Pb, Cu
and Cd (/kg concentrate), cZn is specic production costs for metallic Zn (/kg Zn), C DPj is specic costs for the disposal of residue j (/
kg residue), CINV is specic investment costs for the FLUREC technology (/t y ash), CFLUREC is specic overall costs for the FLUREC technology (/t y ash) and CCP is specic costs for the current practice
of y ash disposal (/t y ash).
2.3. Classication of Zn ows
The classication of Zn present in MSWI residues has been
accomplished in accordance with Lederer et al. (2014) who based
their evaluation framework for anthropogenic resources on
McKelvey (1972). The approach considers both, the economic viability of extracting a secondary raw material from a resource and
producing a tradable good, and the knowledge of the existence of
the resource. For the economic classication, McKelvey suggests
the following terms. Resources are economic or recoverable if they
can be extracted with a prot. Therefore, the production costs must
be below the market price of the product achievable, which means
in our case cZn < pZn. Resources for which the production costs are
higher than the price, but not by more than a factor of 1.5, are marginally economic. Resources above this value are termed as submarginal or subeconomic, whereby according to Lederer et al. (2014) a
threshold factor of 10 times the market price is assumed
99
Table 1
Statistical analysis of y ash (sum of boiler and lter ash, and APC residues in case of dry or semidry APC) amounts (kg/t waste) generated at Waste-to-Energy (WtE) plants with
different ue gas cleaning systems and their respective Zn contents (mg Zn/kg y ash).
Mean
Median
10% quantile
90% quantile
No. of WtE plants
No. of different countries
a
b
Wet
Semidry
Dry
22
22
14
30
53
11
42
40
30
53
33
10
40
39
30
54
11
6
Wet systems
Semidry systems
22,100
19,100
14,000
35,700
16
11
11,000
9700
6700
15,600
14
10
Dry systems
11,700
10,800
7600
18,500
9
6
41,000
42,700
20,900
59,600
15
5
to the y ash and the remaining part to the bottom ash) and the data
given in Table 1, the average content of Zn in the waste feed of European WtE plants have been determined to about 880 110 mg Zn/
kg wet waste. Considering this content and the overall mass of
waste combusted, the following material ow analysis diagram
has been derived (see Fig. 3). In total about 69 9 kt of Zn are annually fed into European waste incineration plants. Almost half of it
(32.5 2.7 kt) accumulates in MSWI residues (bottom ashes and
y ashes from uidized bed combustion) at average concentrations
below 6000 mg Zn/kg ash (see supplementary material). About
17 2.4 kt of Zn are present in boiler and lter ash of grate incinerators equipped with wet APC systems (average Zn content of about
23,000 mg Zn/kg ash) and almost the same amount (18.5 1.8 kt)
can be found in y ashes from dry and semidry APC systems (average Zn content of about 11,000 mg Zn/kg ash).
3.2. Economic evaluation and classication of Zn ows
Based on the material and energy demand of the FLUREC technology and the potential recovery rates for Zn (provided by Boesch
Fig. 3. Annual Zn ows (in 1000 t) through European WtE plants utilizing Municipal Solid Waste MSW and Industrial Waste IW (uncertainties represent the 10% and 90%
condence interval, respectively) red ows indicate ows of MSWI residues with mean Zn contents above 8000 mg Zn/kg (abbreviations used: GI grate incinerator, FBC
uidized bed combustion, APC air pollution control). (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this
article.)
100
Table 2
Economic analysis of Zn recovery from MSWI residues (using the example of lter ash from wet APC systems) applying the FLUREC technology.
Total costs/
savings (per
1000 kg of y
ash)
Mean
Remarks
220
Unit
Mean
sd
Unit
Mean
sd
Data
source
inputs
Fly ash
Zinc content of y ash
HCl (30%) of wet scrubbera
HCl (30%) additional
Sulfuric acid
Hydrogen peroxide H2O2 (50%)
NaOH (50%)
kg
kg
kg
kg
kg
kg
kg
1000
41
550
40
15
65
125
/kg
-0.22
0.02
(1)
1
100
20
1.5
15
12.5
/kg
/kg
/kg
/kg
/kg
0
0.11
0.16
0.30
0.11
0
0.015
0.02
0.030
0.015
(3)
kg
kg
0.4
5
0.08
0.8
/kg
/kg
0.4
1.6
0.1
0.1
(3)
(4)
0.2
8.5
Quicklime
kg
200
20
/kg
0.08
0.01
(2)
16.0
Electricity
kW h
347
18
/kWh
0.094
0.005
(5)
32.6
180
20
(6)
180
(2)
(2)
4.4
2.4
19.1
13.9
kg
800
30
/kg
0.045
0.005
(7)
36.0
kg
0.1
/kg
18
2.8
(8)
18.4
kg
kg
24
9.2
5
1.5
/kg
/kg
0
-1.6
0
0.2
(9)
14.8
Recovery rate of Zn
0.75
0.025
kg
36.1
1.3
64.7
1.8 0.8
Fig. 4. Specic costs (+) and revenues/saving () of the FLUREC technology when treating lter ash from wet APC systems with an average Zn content of 41,000 mg/kg y ash.
101
it becomes obvious that avoided costs for the current disposal practice of y ash as well as investment costs for the technology are most
signicant for the economic viability (see Fig. 4). The contribution of
revenues realized by metallic Zn recovery is below 17% of the total
gross revenues, which amount to approximately 300/kg y ash.
For the other y and bottom ashes of European WtE plants, specic production or recovery costs of Zn are much higher (see Fig. 5).
This can be attributed on the one hand to the lower Zn content in
these ashes and on the other hand signicant amount of HCl is
required for plants with dry or semi-dry APC systems. Moreover
recovery costs for Zn contained in non-hazardous waste, such as
y ash from FBC or bottom ash from grate incineration, are distinctly
higher, as the potential savings for avoided disposal costs after treatment are minor. Detailed information about the underlying data for
the economic evaluation of Zn recovery from different types of y
ashes and bottom ashes is provided in supplementary material.
Combining information about the size of Zn ows, incl. their
uncertainties (see Fig. 3) and the specic recovery costs (see
Fig. 5) allows classifying Zn ows in accordance to the classication scheme for mineral resources (McKelvey, 1972). The result
of this classication (Table 3) demonstrate that the total size of
the identied Zn ows in European MSWI residues is 69,000 t/a.
Based on the average market price for Zn over the last 5 years
Fig. 5. Specic recovery costs for zinc (given in /kg Zn) from different MSWI residues.
Table 3
McKelvey diagram for annual Zn ows (in t/a) in European MSWI residues (the uncertainty ranges of the estimates form the basis for the distinction between demonstrated,
inferred, and potentially undiscovered resources).
Identied resources
Demonstrated
Inferred
Economic
Marginally economic
Subeconomic
Other occurrences (low grade)
Low-grade materials
0a
4100b
6800b
47,400
0a
700b
1100b
7900
Total
69,000
0a
700b
1100b
7900
9000
An economically viable recovery of Zn from y ashes would (at current market prices) only be possible at Zn contents above 53,000 mg/kg ash or avoided costs for the
disposal of untreated ashes of more than 230 /ton ash.
b
Assuming that at 50% of all WtE plants with wet APC systems lter ashes and boiler ashes can be separately collected and that technical recovery rates of Zn amount to
75%.
102
Acknowledgments
The presented work is part of a large-scale research initiative on
anthropogenic resources (Christian Doppler Laboratory for Anthropogenic Resources). The nancial support of this research initiative
by the Austrian Federal Ministry of Science, Research and Economy
and the National Foundation for Research, Technology and Development is gratefully acknowledged. The authors also gratefully
acknowledge the support of Karin Karlfeldt Fedje and Aurore De
References
Abe, S., Kagami, T., Sugawara, K., Sugawara, T., 2000. Zinc and lead recovery from
model ash compounds. In: Second International Conference on Processing
Materials for Properties, pp. 733736.
Astrup, T., 2008. Management of APC residues from W-t-E Plants An overview of
management options and treatment methods. International Solid Waste
Association (ISWA), Copenhagen, p. 116.
Aubert, J.E., Husson, B., Vaquier, A., 2004. Use of municipal solid waste incineration
y ash in concrete. Cem. Concr. Res. 34, 957963.
Aubert, J.E., Husson, B., Sarramone, N., 2007. Utilization of municipal solid waste
incineration (MSWI) y ash in blended cement: Part 2. Mechanical strength of
mortars and environmental impact. J. Hazard. Mater. 146, 1219.
Auer, S., Kuzel, H.J., Pollmann, H., Sorrentino, F., 1995. Investigation on Msw y-ash
treatment by reactive calcium aluminates and phases formed. Cem. Concr. Res.
25, 13471359.
Boesch, M.E., Vadenbo, C., Saner, D., Huter, C., Hellweg, S., 2014. An LCA model for
waste incineration enhanced with new technologies for metal recovery and
application to the case of Switzerland. Waste Manage. 34, 378389.
Bontempi, E., Zacco, A., Borgese, L., Gianoncelli, A., Ardesi, R., Depero, L.E., 2010. A
new method for municipal solid waste incinerator (MSWI) y ash inertization,
based on colloidal silica. J. Environ. Monit. 12, 20932099.
Brunner, P.H., Mnch, H., 1986. The ux of metals through municipal solid waste
incinerators. Waste Manage. Res. 4, 105119.
Brunner, P.H., Rechberger, H., 2004. Practical Handbook of Material Flow Analysis.
CRC Press LLC, Boca Raton, Florida.
Bhler, A., Schlumberger, S., 2010. Schwermetalle aus der Flugasche
zurckgewinnen: Saure Flugaschenwsche FLUWA Verfahren, ein
zukunftsweisendes Verfahren in der Abfallverbrennung (Recovering Heavy
Metals from Fly Ash: Acidic Fly Ash Scrubbing FLUWA, a Trendsetting
Procedure in Waste Incineration). KVARckstnde in der Schweiz Der
Rohstoff mit Mehrwert (MSWI Residues in Switzerland A Resource with
Added Value). Swiss Federal Ofce for the Environment (FOEN), Bern.
CEWEP, 2011. Map of European Waste-to-Energy plants in 2011. Confederation of
European Waste-to-Energy Plants, Brussels. <http://http://www.cewep.eu/
information/data/studies/index.html> (accessed 28.09.14).
Chiang, K.Y., Jih, J.C., Chien, M.D., 2008. The acid extraction of metals from municipal
solid waste incinerator products. Hydrometallurgy 93, 1622.
Dabo, D., Badreddine, R., De Windt, L., Drouadaine, I., 2009. Ten-year chemical
evolution of leachate and municipal solid waste incineration bottom ash used in
a test road site. J. Hazard. Mater. 172, 904913.
De Boom, A., Degrez, M., Hubaux, P., Lucion, C., 2011. MSWI boiler y ashes:
magnetic separation for material recovery. Waste Manage. 31, 15051513.
Eurostat, 2013. Electricity Prices By Type of User. <http://epp.eurostat.ec.europa.eu/tgm/
table.do?tab=table&plugin=1&language=en&pcode=ten00117> (accessed 15.06.14).
Eurostat, 2014. Municipal Waste Statistics. <http://epp.eurostat.ec.europa.eu/
statistics_explained/index.php/Municipal_waste_statistics> (accessed 28.09.14).
Ferreira, C., Jensen, P., Ottosen, L., Ribeiro, A., 2005. Removal of selected heavy
metals from MSW y ash by the electrodialytic process. Eng. Geol. 77, 339347.
Hallgren, C., Strmberg, B., 2004. Current methods to detoxify y ash from waste
incineration. Svensk Fjrnvrme AB, TPS.
Hjelmar, O., 1996. Disposal strategies for municipal solid waste incineration
residues. J. Hazard. Mater. 47, 345368.
ISWA, 2006a. Waste-to-Energy State-of-the-Art-Report, Statistics,
fth ed.
International Solid Waste Association, Copenhagen, p. 232.
ISWA, 2006b. Management of Bottom Ash from WTE Plants An Overview of
Management Options and Treatment Methods. International Solid Waste
Association Working Group Thermal Treatment, Copenhagen, p. 86.
ISWA, 2013. Waste-to-Energy State-of-the-Art-Report, Statistics,
sixth ed.
International Solid Waste Association, Vienna, p. 210.
Jakob, A., Stucki, S., Struis, R.P.W.J., 1996. Complete heavy metal removal from y
ash by heat treatment: inuence of chlorides on evaporation rates. Environ. Sci.
Technol. 30, 32753283.
Karlfeldt Fedje, K., Ekberg, C., Skarnemark, G., Steenari, B.-M., 2010a. Removal of
hazardous metals from MSW y ashan evaluation of ash leaching methods. J.
Hazard. Mater. 173, 310317.
Karlfeldt Fedje, K., Rauch, S., Cho, P., Steenari, B.-M., 2010b. Element associations in
ash from waste combustion in uidized bed. Waste Manage. 30, 12731279.
Karlfeldt Fedje, K., Ekberg, C., Skarnemark, G., Pires, E., Steenari, B.-M., 2012. Initial
studies of the recovery of Cu from MSWI y ash leachates using solvent
extraction. Waste Manage. Res. 30, 10721080.
Karlfeldt Fedje, K., Andersson, O. Modin, P., Frndegard, P., Pettersson, A., 2014.
Opportunities for Zn recovery from Sweidsh MSWI y ashes. 2nd Symposium
103
Nowak, B., Aschenbrenner, P., Winter, F., 2013. Heavy metal removal from sewage
sludge ash and municipal solid waste y ash a comparison. Fuel Process.
Technol. 105, 195201.
Quina, M.J., Bordado, J.C., Quinta-Ferreira, R.M., 2008. Treatment and use of air
pollution control residues from MSW incineration: an overview. Waste Manage.
28, 20972121.
Schachermayer, E., Bauer, G., Ritter, E., Brunner, P.H., 1996. Entwicklung einer neuen
Methode, um aus den Produkten der Mllverbrennungsanlage Spittelau
kostengnstig die Vernderung der Zusammensetzung des Wiener Mlls zu
bestimmen (A new cost effective method for determining the composition of
Municipal Solid Waste in the city of Vienna using information about the
residues of the waste incinerator Spittelau). Institute for Water Quality and
Waste Management, Vienna University of Technology, Vienna.
Schlumberger, S., 2010. Neue Technologien und Mglichkeiten der Behandlung von
Rauchgasreinigungsrckstnden
im
Sinne
eines
nachhaltigen
Ressourcenmanagements (New Technologies and Possibilities for the
Treatment of Flue Gas Cleaning Residues to Achieve Sustainable Resource
Management). KVA Rckstnde in der Schweiz Der Rohstoff mit Mehrwert
(MSWI Residues in Switzerland A Resource with Added Value). Swiss Federal
Ofce for the Environment (FOEN), Bern.
Sorlini, S., Abb, A., Collivignarelli, C., 2011. Recovery of MSWI and soil washing
residues as concrete aggregates. Waste Manage. 31, 289297.
Spatari, S., Bertram, M., Fuse, K., Graedel, T.E., Shelov, E., 2003. The contemporary
European zinc cycle: 1-year stocks and ows. Resour. Conserv. Recycl. 39, 137
160.
Van Gerven, T., Cooreman, H., Imbrechts, K., Hindrix, K., Vandecasteele, C., 2007.
Extraction of heavy metals from municipal solid waste incinerator (MSWI)
bottom ash with organic solutions. J. Hazard. Mater. 140, 376381.