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FG Cleaning Waste
FG Cleaning Waste
FG Cleaning Waste
Ammonia
Natural
H2O gas
Activated
coke
To incinerator
Hg-bearing
activated carbon
Heavy-metal
condensate 3 Gypsum 6
Glass
granules 30 Quantity in kg per tonne of waste
Hydrochloric acid 15 Lime sludge
TCR process, with resource recovery, for flue-gas cleaning in waste incineration plants 1
process, which it calls Total Cleaning and bag filter, where the dust is removed. The containing heavy metals is also removed
Recycling, or TCR. high efficiency of the bag filter has a very with the dust.
As the process schematic 1 of the positive effect on the performance of the In the first scrubber, quenching is fol-
modular TCR facility shows, the flue gas scrubbing stages, and especially on the lowed by wash-out of the hydrochloric acid
first passes from the incineration grate recovery of resources from the scrubbing (HCl) under acidic conditions. The second
to the heat-recovery boiler and then to a liquids. The majority of the particulate scrubber absorbs the sulfur dioxide. This
solves the initial problem of removing the
principal acidic constituents of the flue
Pollutants TA Luft ’86 17th BlmSchV EU Guideline The scrubbing stages are followed by
a second bag filter in which a process
Dust 30 10 10 known as filsorption – a name taken from
Carbon monoxide 100 50 50
filtration and adsorption – takes place. The
Organic materials (C tot) 20 10 10
Sulfur oxides as SO2 100 50 50 filsorption filter uses a mixture of activated
Gaseous anorg. comp. of chloride as HCl 50 10 10 coke and lime hydrate, and is largely
Gaseous anorg. comp. of fluorine as HF <5 1 1 responsible for the exceptionally good
Nitrogen oxides as NO2 500 200 –
clean-gas data. It is especially good at
Cd, Tl Y 0.2 0.05 0.05 adsorbing dioxins and furans as well as any
Hg 0.05 0.05 residual mercury left after scrubbing, while it
Sb, As, Pb, Cr, Co, Cu, Mn, Ni, V, Sn – 0.5 0.5 also removes any harmful acids, dust and
Dibenzodioxins/-furans
heavy metals still present. As a result, clean-
in ng/Nm3, dry, 11 % O2 – 0.1 0.1
(Toxic equivalent (TE) in accordance with NATO-CCMS gas values even lower than the detection
limits are achieved.
Filsorption is offered by ABB as its pre- • The sorbent material used in the filsorp- Further development
ferred alternative to coke bed filters. With tion process is led directly back to the of the dual-alkali process
reactors containing several hundred cubic furnace in order to destroy the dioxins ABB has developed a particularly interesting
meters of activated coke, the latter repre- and furans contained in it. Alternatively, variation of the TCR process for washing
sent a genuine fire hazard. Both processes the material can be vitrified together with out the harmful acidic gases. It combines
employ the highly efficient technology the dust collected in the first filter. the ABB spray scrubber 2 with the dual-
known generically as adsorption. The TCR concept is so new that all the alkali process developed by ABB especially
A direct comparison shows the filsorp- modules making up the facility could not yet for waste incineration plants.
tion process to be better not only in terms of be installed and used together in the same The state of the art is to separate the
safety but also with regard to dust, heavy incineration plant. However, each individual acidic gases hydrogen chloride (HCl) and
metal and carbon monoxide emissions. module has been tested in the field on a sulfur dioxide (SO2) in consecutive scrub-
With regard to all the other components, the large scale. The flue-gas cleaning system, bing stages. Prior to the absorption (ie, dur-
two processes perform at similar levels. for example, is operating in several plants, ing quenching) the flue gas is cooled to its
The denox stage, which employs selec- and reliable emission data with this system wet-bulb temperature by co-current spray-
tive catalytic reduction (SCR), is usually is now readily available. ing of a liquid into the flue-gas flow. In the
positioned by ABB at the end of the flue-
gas cleaning process. The filsorption filter
upstream provides optimum protection for ABB spray scrubber used in combination with the dual-alkali process 2
for washing out harmful acidic gases
the catalyst. Since the denox process can
take place at a temperature of 200 ˚C or 1 Quenching stage 2 HCl stage 3 SO2 stage
lower, long residence times are possible.
Reasons can also be given, however, for
installing the catalyst immediately after the
scrubbers. In this case, a combined catalyst
is used. It first reduces the nitrogen oxides
(NOx) and then oxidizes the organic sub-
stances, in particular the dioxins and furans.
3
The operating temperature with this con-
figuration is about 300 ˚C. Its advantage is
that the dust collected in the filter is prac-
tically free of dioxins.
The residues produced by flue-gas clean-
ing are treated in different process stages:
• The fly ash from the incinerator and the
dust collected in the first bag filter are 2
passed through the DEGLOR process
[1], in which an electrically heated fur-
1
nace melts them into a harmless glassy
slag suitable for use in, eg, sand-blasting
or road construction, plus a ‘heavy metal
concentrate’ which can be processed in
specialized metallurgical plants.
• The draw-off from the scrubbing process
can be treated in different stages (distil-
lation, evaporation, crystallization, filtra-
tion, etc) to recover valuable resources.
Some possible products are hydrochloric
acid, sodium chloride for chlorine-
alkali electrolysis, and gypsum (eg, for
use in manufacturing wall-board).
Flue-gas
inlet
Gypsum
dewatering stage Gypsum
Flow chart of the dual-alkali system developed by ABB. Gypsum is precipitated by this patented process. 3
first scrubber the HCl in the flue gas is uses limestone rather than a caustic soda Important benefits in respect of the SO2
absorbed by an acidic solution comprising solution. Another reason for this preference separation are:
HCl and water. At the top of the HCl stage is that many operators prefer gypsum • Since a clear solution is used, the resis-
very fine droplets of the scrubbing agent are (CaSO4 • 2 H2O) to sodium sulfate as an tance to mass transfer during the ab-
sprayed into the gas flow in the counter-cur- end-product, since the former has more sorption process and oxidation to sulfate
rent direction. The diluted hydrochloric acid commercial uses. is very low.
that is produced collects at the bottom of Although the above considerations • The ratio of the liquid to flue gas in the
the tank and is pumped back to the nozzle weigh heavily, scrubbers using a caustic scrubber is small.
level in the circuit. The scrubbing liquid is soda solution have several clear technologi- • There is only a small pressure drop; the
drawn off and replaced by fresh water cal advantages over those which use lime- residence time is short.
according to the acid concentration. The stone, particularly in the areas of operation To be able to take advantage of the bene-
drawn-off liquid can be processed to obtain and reliability. These benefits can be sum- fits of a scrubber that uses a caustic
concentrated hydrochloric acid, etc. marized as follows: soda solution and produce gypsum at
In the second scrubbing stage the sulfur • All feed material and reaction products the same time, ABB has further develo-
dioxide is absorbed by mixing caustic soda are in the form of aqueous solutions; no ped the so-called dilute mode dual-
or lime hydrate (calcium hydroxide) with the solids are involved. alkali process, modifying it for flue-gas
scrubbing agent to keep it neutral. Use • No protection against erosion has to be cleaning in waste incineration plants. In
of crushed limestone (CaCO3) as a neutral- provided. this process 3 , which has been pat-
izing agent is also possible. Continuous • Since there are no sediments, the liquid ented, the solution drawn off from the
measurement of the pH value is necessary does not have to be circulated to prevent neutral SO2 stage of the scrubber has
in this stage. sedimentation. lime hydrate (Ca(OH)2) added to it.
The type of neutralizing agent chosen will • Only minimal maintenance of the Through this simple ion interchange,
generally depend on the overall costs. Cal- demister is required. gypsum is precipitated and the caustic
cium hydroxide and limestone being much • The alkaline stage can be installed simply soda solution is regenerated:
cheaper than caustic soda, incineration on top of the acid stage, saving floor
plant operators often prefer a scrubber that space as well as costs. Na2SO4 + Ca(OH)2 ––> CaSO4 + 2NaOH
Although it is usual for the lime hydrate to tation of the sulfate). One of the main goals plant. In addition, the theoretical risk of the
be added in the dry state, lime milk or even of the development work was to ensure that gypsum quality varying was far greater, due
slaked quicklime can also be used. the process has only a minimal effect on the mainly to the operating conditions in a
In a second stage, a very small quantity availability and operation of the scrubber. waste incineration plant fluctuating more
of soda (Na2CO3) is added to the solution This is often the key to reliable operation of strongly than in a power station, where the
regenerated with lime hydrate in order to the incineration plant. The separate process quality of the coal remains relatively con-
replace the Na+ ions lost during the pro- stages also provide numerous possibilities stant. The recovery of products from waste
cess. The use of soda, which is relatively for optimizing plant operation, for example incineration is also a political issue, since
cheap, also has the effect of softening the through the installation of intermediate stor- they are automatically considered to be
regenerated solution according to age tanks or the use of parallel or common ‘dirtier’ than the same material originating
systems for more than one incineration line. from other sources. The goal was to
Na2CO3 + Ca2+ ––> CaCO3 + 2Na+ The scrubber may also be operated with achieve a gypsum quality that would allow
just fresh caustic soda solution if required. disposal in Class I landfills as per the
before it passes back to the scrubber, thus An installation of the type described has German ‘TA Siedlungsabfall’ decree. This
reducing the risk of sedimentation in the been built in the Hobro waste incineration reduces the cost of landfilling substantially,
scrubber cycle. plant in Denmark, allowing full-scale field compared with the alternative of gypsum
The calcium carbonate which is pro- experience to be gained for the first time disposal in Class II landfills, as is usually
duced is precipitated, separated from the with this technology. necessary when the calcium salts come
clear regenerated solution and re-used in Initially, the quality of the gypsum pro- from a treatment plant in which the waste-
the effluent treatment plant. duced in the Hobro plant was evaluated water is still contaminated with heavy
The regeneration process for recovering under the assumption that it would probably metals.
the caustic soda solution takes place in a be disposed of in landfills. This assumption The results from the Hobro demonstra-
separate plant and therefore has no in- was made on the basis of the quantity pro- tion plant were promising from the begin-
fluence on the availability of the scrubber duced in a waste incineration plant usually ning, and gypsum suitable for Class I landfil-
and the chemical reactions. Oxidation of the being much smaller than the amount pro- ling could be produced immediately and
remaining sulfite to sulfate takes place in a duced, for example, in a coal-fired power without problems. The requirements for
separate oxidation tank located in the outlet
of the scrubber’s SO2 stage. Complete
oxidation is easily achieved since both the Separation of sulfur dioxide with the ABB spray scrubber 4
sulfite and the sulfate are present in the (N.tr. = standard condition, dry gas)
dissolved state.
Green SO2, inlet Red SO2, outlet Blue SO2, theoretical equilibrium
Dual-alkali system
The experience gained in the Hobro inciner-
ation plant mainly concerns the dual-alka-
li system, in which the entire liquid flow from
the scrubber is treated. The tests have
shown that the scrubber and regeneration
system can handle all the operating con-
ditions that could arise in practice. Full-scale
operation was especially important for the
way it helped with the design and fine-tun-
ing of the control system.
Operation on this scale is also necessary
Filsorption stage with scrubber using a sodium hydroxide solution, 5 to obtain reliable mass balances for the
as retrofitted recently in the waste incineration plant at Zirndorf in Germany
combined scrubber and regeneration
system. Tests were carried out both with dry
construction-quality gypsum could also be Operating experience in slaked lime and lime milk.
fulfilled from the start. At about the same the Hobro waste incineration plant Full-scale trials are also important as they
time, several countries began to require provide experience with operation of the in-
waste incineration plants to produce recy- Scrubber dividual components. The only component
clable end-products only. In view of this, The scrubber, which uses a caustic soda that has had to be replaced during the pro-
special emphasis was placed on demon- solution, is a proven ABB design with more gramme is the gypsum dewatering system.
strating the Hobro plant’s capability for pro- than 65 modules; 15 of these are part of the Because the gypsum crystals obtained with
ducing construction-quality gypsum (eg, for waste incineration flue-gas cleaning pro- the new system are considerably larger than
wall-board). cess. Since the scrubber was optimized for those obtained with similar systems and
Tables 2 and 3 compare the achieved this application from the start, emission with the pilot installation in the ABB re-
gypsum quality with the requirements for values are very low 4 . Features that make search center in Växjö, Sweden, the drum
Class I and II landfilling as well as for wall- a decisive contribution to the good results filter had to be replaced by a band filter. The
board manufacture. It can be seen that all include the design of the nozzle lances and advantage of the larger crystals in terms of
the requirements are easily satisfied. the intermediate bottoms. dewatering, washing properties and gyp-
München Süd, Germany’s first district heating plant based on waste incineration to be equipped with the SCR denox system 6