DISPOSAL OF MWSI RESIDUE

Legal allocation of solid residues for disposal

Recycling of solid residues within construction industry is regulate by assignment criteria (Z) of the states
committee on waste (in German: Landerarbeitsgemeinschaft Abfall (LAGA) (cf. table 1) *3+. Landfilling
according to German guidances (TASI = TA s=Seidlungsabfall and TA Abfall) corresponds to
assignment classes Z 3 to Z 5. Recycling of mineral residues is defined by classes Z 0 to Z 2.

Construction of landfill sites fulfilling classes Z3 to Z5 is discussed in a separated script. Regulations
contain different criteria for solids and eluate. Eluate criteria are comparatively presented in table 2.
Limited placement with defined technical measures (Z 2) represents the lowest level of recycling.
Generally, criteria of class Z 2 consider organic constituens and heavy metal contents of the solid (cf.
table 4) as well as different parameters of eluate (cf. table 2). An exception to the rule is for HWI bottom
ashes, which must be analysed only with respect to organic contents (TOC < 1 wt.-%: 3 mg/kg) of the
solid and eluate criteria (Z 2
MWI
in table 2).
Limited placement with defined technical measures (Z 2) represents the lowest level to recycling.
Generally, criteria of class Z 2 consider organic constituents and heavy metal contents of the solid (cf.
table 4) as well as different parameters of eluate (cf. table 2). An exception to the rule is for HWI bottom
ashes, which must be analysed only with respect to organic contents (TOC < 1 wt.-%: 3 mg/kg) of the
solid and eluate criteria (Z 2
MWI
in table 2).
Figure 1 shows recycling of MSWI bottom ashes as a bearing layer in road construction. Impermeable
road surface and mineral sealing protect bottom ash against contact with water. Additionally, placement
is only permitted in areas showing low groundwater level (no water inlet from below) underneath of
soils retaining soluable pollutans.


Properties of solid MSWI residues
Bottom ashes
As the largest residues fraction, bottom ashes constitue 25-35 wt.-% of waste input. Main constituents
are silicon, iron, aluminium and alkali oxcides (cf. table 3). In addition, they contain heavy metals (cf.
table 3 and 4) and unburned organic compounds as minor components.
Heavy metal concentrations of MSWI-bottom ashes clearly exceed guide values of arable soils [6].
Comparison of bottom ashes and earths crust shows enrichment of pollutans, e.g. heavy metals, in the
ashes. Uncontrolled release to biosphere implies danger for human beings and environment, so
mobillisations must be prevented by suitable measures (cf. chapter 4). From there, MSWI bottom ash
recycling requires well definied safety measures (Z 2). In some cases the content even exceed the limits
of Z 2 (cf. table 4), so in any case an analysis is required.



It should be pointed out, that dioxinds and furans in bottom ashes are low in content. Concentrations
measured (7.2 25 ng of toxicity equivalents (TE)/kg ash) remain below recommended limits of
childrens soils (100 ng TE/kg) [14].
Leachated concentrations of MSWI bottom ashes fulfill assignment criteria of class Z 2 only after ageing
of ash (cf. table 5).
Fly ash/Filter dust
Similarly to bottom ashes, fly ash and filter dust consist of a SI-Fe-Al-Ca-matrix, where heavy metals and
organic compounds are condensed. Their content noticeably exceeds limits of Z 2 (cf. table 4).
Additionaly, fly ash and filter dust are contaminated by dioxids and furans (up to 12700 ng TE/kg [1]),
which may be generated in the flue gas stream by de-novo-synthesis. That means, precursors are
synthesized in a temperature range of 250-450
0
C accelerated in presence of catalytic metal chlorides,
oxygen and large surfaces of fine-grained ashes. If the flue gas has a sufficient residence time in this
temperature range, dioxins and furans may be generated in large quantities adsorbing on fly ash and
filter dust.
Besides high organic contents, ashes and dust may contain high concentrations of heavy metals (Pb, Zn).
Obviously there is no increased elution by the DEV-S4 test (cf. table 5), because the metals are
participated as solid hydroxides or carbonates under test conditions (alkaline pH).
Scrubber salts
Scrubber salts precipitating at flue gas cleaning mainly consist of calcium, sodium, magnesium, and
potassium-chlorides (cf. table 3). They also contain dust particles leading to moderate content of silicon,
aluminium and iron, as well as high amounts of heavy metals (cf. table 3). Scrubber salts endanger the
environment, because heavy metal compounds are frequently readily soluable.
Residues of melting processes
New processes of thermal MSW treatment, e.g. Thermoselect-process and Schewel-Brenn-
Verfahren, operate at high temperatures, so that heavy metals evaporate and minerals and metallic
residues melt. Moreover, in case of the Thermoselect-process, the mineral and metallic fraction are
separated by density, for that reason yielding granulated mineral residues have low heavy metal
concentrations compared to MSWI bottom ashes (cf. table 4).
Fusion processes for fly ashes and filter dust operated at the same principle but without separation of a
metallic fraction (cf. chapter 4.6). Thats why the fusion granulate, as exemplary presented in table 4,
has high zinc concentrations.
Granulated residues consist of a glass matrix immobilizing heavy metals. Therefore, heavy metal content
of leachate according to German DEV-S4 elution test near or below detection limits (cf. table 5).
Treatment of residues
An overview of different treatment processes advantages for special residues is shown in table 6. In the
following, only most important processes will be discussed.

Mechanical treatment
Process
Before mechanical treatment, bottom ashes are covered and stores for 2-3 weeks to reduce humidity by
evaporation and generation of leachate.
Treatment is devided into various steps, like separation of scrap and sieving. Oversized material of first
sieving is crushed by impact crusher and then sieved again.

After mechanical treatment, bottom ashes are aged by storage for 3 months. At this time, chemical
reactions cause volume change and heat release, which must be finished before recycling. Additionally,
ageing improves elution behavior by take-up of carbon dioxide:

Table 7 illustrates the impact of leachate from fresh and MSWI bottom ashes aged for 3 months,
according to the German DEV-S4 elution test
In Germany, the DEV-S4 procedure is the standard elution test for landfill and recycling criteria,
simulating leaching 24 hours by distilled water. Here, leachate pH has significant influence on
mobilisatin of ash components. Due to solution of alkaline constituents, pH of DEV-S4 leachates reaches
a value between 12 and 13. At this pH, must heavy metals precipitate as hydroxides or carbonates. Still,
measurable leaching is caused by formation of soluable hydroxo complexes or oxo anions. Drainage
water of stored MWI bottom ashes has a similar pH, so leaching behavior comparable to DEV-S4 test
may be assumed. Thus, drainage water is contaminated with salts and heavy metals.
Leaching of soluable constituens initially decreases because of a lowered pH (11-12). Decrease of pH is
caused by CO
2
absorption, pH decreases further (pH<7), leading to an increase of heavy metal leaching.
In mono landfills of MSWI bottom ashes, this effect is to be expected after centuries.
Table 7 cleary shows bottom ashes meeting criteria of German Landfill classes I and II in most cases.
Only lead concentrations of fresh bottom ashes exceed limits, because lead forms very soluble
compounds at alkaline pH. Treated and stored bottom ashes comply with criteria (Z 2) except for two
lead values (cf. table 7).
Operation
Recycling of bottom ashes is only permitted, if water inlet prevented by technical measures (cf. chapter
5). Leachate of mechanical ash treatment has to be collected and cleaned according to the state of the
art.
Solidification
Solidification is essentially suitable for residues with high silicon and calcium contents, e.g. ashes and
dust. Besides self solidification after addition of water, cement is mixed to ashes and dust. Solidification
is based on puzzolan reaction of calcium hydroxide, silicate and water to calciumsilicate hydrates (CSH).
CSH-compounds are a storing mineral fixing heavy metals by following mechanisms:
Insertion in thr lattice
Chemical bonding on hydrate surfaces
Physical adsorption on hydrate surfaces
Additionally, CSH-compounds prevent contact of water and heavy metals.
3R-Process
By the 3R-process (in German RauchgasReinigung mit Ruckstandsbehandlung *2]: flue gas cleaning
including residues treatment), heavy metals are washed from filter dust by acid solution. For that
purpose, effluent from the acid flue gas scrubber of an MSWI-plant may be appropriate, being filtered
and mercury and other heavy metals taken off by an ion exchanger (cf. figure 3). After washing, the
suspension enters a vacum band filter. The filtrate is cleaned via usual scrubber water treatment,
concentrating heavy metals into reaction salts. Additionally, 20% of matter is soluble in water, so it must
deposited with reavtion salt.
After filtering, filter dust is mixed with a binder, pelletiesed and re-direct to MSWI. Pelletisation is
necessary to prevent entraining by the flue gas stream. During inceneration, organic compounds
(including dioxins/furans) are destroyed, and heavy metals evaporate.
Hagenmaier drum
In the so-called Hagenmaier drum, fly ashes and filter dust are thermally treated at low temperatures
(T= 250-480
0
C) and lack of oxygen for 30-60 min [16]. There, de-novo-synthesis is reserved, so more
than 97% of dioxins and furans are destroyed. Disposal situation is same as before, because heavy metal
contamination remains constant.









Fusion
Fusions processes are suitable for bottom ashes, fly ashes and filter dust, being melted at high
temperatures (T1300
0
C). addition of aggregates decreases melting temperature, change slag viscosity
and stabilises the glass matrix. At high temperature, organic pollutants are completely destroyed and
heavy metals evaporate. In addition, separation of mineralogical and metallurgical melts is possible by
density. Thats why fusion product may contain either low (Thermoselect in table 4) or high quantities
of heavy metals (granulate in table 4). The fusion process is intergrated in or subsequent of waste
inceneration (cf. figure 4).
Advantage of fusion processes is in destruction of toxic organic compounds and separation of heavy
metals. Additionally, fast cooling of the melt generates a granulate immobilizing heavy metals in glassy
matrix. This effect is clearly shown in table 5 by low heavy metal leaching from Thermoselect and
Schewel-Brenn residues as well as by filter dust granulate (compare chapter 3.1).

Disavantage of subsequent fusion processes is in high expenditure of energy to re-heat residues. In
Germany, subsequent fusion processes are not competitive at the present, because costs of other
disposal channels are lower. Moreover, exhaust gas must be cleaned because of evaporation of heavy
metal chlorides. Fusion processes should be integrate into an existing MWI-plant, allowing joint use of
gas cleaning systems.


Disposal
Bottom ashes
Recycling of MSWI bottom ashes may be divided into two fields of aplication: On the hand recycling as
building materials, on the other hand as a high-quality product for special application. In Germany, at
the present MWI bottom ashes are only recycled as building materials:
1. In road construction after mechanical treatment and ageing,
2. As a filling material of salt and coal mines,
3. In landfill construction frequently after mechanical treatment and ageing.
High-quality recycling of MSWI bottom ashes may be as an aggregate of concrete, tiles or paving stones,
as a cement additive, as a mineral insulator, or as a jet medium [15]. Market situation of secondary
building materials in Germany (1991) is illustrated in figure 3.
Figure 3 shows MWI bottom ashes (2,4 Mio. T) having a part of 1,4% of the market of 177 Mio. t/a
(1991). In the market, ca. 100 Mio. t/a of secondary building materials was not recycled in 1991. The
recycle ratio of MWI-bottom ashes actually amounts to 60%. An increase of recycling seems to be
impossible with regard to huge competition: Comparatively small quantities of MSWI bottom ashes of
bad image complete with a huge amount of clean competitors. Therefore, an increase of recycling
ratio may only be reached by new, high-grade and competitive applications. Remaining 40% of MWI
bottom ashes are deposited off landfills.



Fly ash and scrubber residues
Flu ashes precipitate in the boiler and in filters. They consitute approx. 2.5% of waste input. With
respect to main compounds, fly ashes are similarly to bottom ashes. They are also consisting of a Si-Fe-
Al-Ca-matrix, where heavy metal chloride and organic compounds are condesed. Heavy metal chlorides
are usually readily water soluble. From there, fly ashes may only be deposite in underground depots. For
some years, they are also used as a filling material in hard coal and salt mines. Solidification and fusion
procedures achieving immobilisation of pollutants contained in flu ashes, have not established because
of high costs /17/.
Wash water of srubbers is cleaned by procedures described in the paper concerning CPB-treatmenr, and
then supplied to the scrubber again. Scrubber residues, as an example salts and gypsum, hold about
4.5% of waste input. Marketing of reaction salts is not common in practice, too.
Active carbon and ceramic catalysts
In HWI-plants equipped with activated coal and coke filters, 0,4% of loaded activated coke arises,
related to the waste input. Loaded coke is combusted in the rotary kiln /17/. Due to an effective sink of
heavy metals by slag, fly ashes and scrubbers and due to destruction of organic compounds during
inceneration, accumulation of pollutants does not occur. Ceramic catalysts from nitrogen removal have
a serviceable life of several years and are then supplied to the rolary kiln for combustion likewise.
Overview of municipal solid waste solid waste inceneration (MSWI) residue management