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tween the two. The total reaction is rather
Intervex – Ein neues Verfahren zur The basic process sluggish and the process demands large reac-
Rauchgasentschwefelung tion volumes.
In the Intervex desulphurisation process, gran- If however, the limestone is just moistened
Ein neues Verfahren zur Rauchgasentschwefe-
lung wird vorgestellt. In einen Reaktor werden ular limestone is used as reactant, water is with water, and the flue gas is led in contact
Rauchgase im Gegenstrom durch ein körniges sprayed over the granular bed and the flue gas with it, the reaction will be very fast. We ob-
Kalksteinbett geleitet. Wasser wird oberhalb is led upwards through the bed. served this during our development work and
des Bettes gleichmäßig versprüht. Der Kalk- since then, we have tried to design a desul-
stein wandert langsam von oben nach unten The reaction between limestone, CaCO3 and
und der Grobanteil wird rezirkuliert. Schwe- sulphur dioxide SO2 takes place in the pres- phurisation process for this fast reaction.
feloxide aus dem Rauchgas bilden Calcium- ence of water: In our first process, we used a limestone bed
sulfit und Calciumsulfat und werden mit dem
Wasser ausgewaschen. CaCO3 + SO2 + 2 · H2O = as heat exchanger, i.e. two parallel reactors
Eine erste Pilotanlage für ein 20-MW-Kessel ist CaSO3 · 2H2O + CO2 (1) were applied, which alternatively cooled flue
seit mehreren Jahren in Betrieb. Für diese gas and heated combustion air. When the flue
kann auf interessante Betriebsergebnisse ver- In the presence of oxygen, the calcium sul- gas was cooled by limestone, a very thin layer
wiesen werden. phite will oxidise to calcium sulphate, gyp- of water condensed on the stone surface, and
So kann ein hoher Abscheidegrad von Schwe- sum: in this layer, sulphur oxide contained in the
fel, Chlor, Fluor und Flugasche bei geringem
Druckverlust festgestellt werden. Der Ausnut- CaSO3 · 2H2O + ½ O2 = CaSO4 · 2H2O (2) flue gas immediately formed calcium sulphite,
zungsgrad des Kalksteins liegt bei 75 %. Der i.e. gypsum. The process had two functions:
Kalkstein ist preiswert und die Investitionskos- The oxidation is rapid in acidic environment.- desulphurisation and recovery of heat from
ten für die Anlage sind niedrig. the flue gases. We could regain heat from the
To avoid that a layer of calcium sulphate is
formed on the limestone, a small content of flue gases down to a temperature about 50 °C.
chloride ions should be present in the water. This double function made the process quite
The chloride ions react with the limestone to attractive.
form calcium ions in the spray water, and In the process, the flue gas was led upwards
these calcium ions react with sulphur dioxide through the limestone bed whereas the lime-
to form calcium sulphite in the water phase: stone was transported downwards, creating a
counter flow process. From the bottom of the
CaCO3 + 2HCl = reactor, the exit stone was led to a tumbler to
Ca2+ + CO2 + H2O + 2Cl- (3) wear off sulphite. The cleaned stones were
transported to the top of the reactor and again
SO2 + 3H2O = 2H3O+ + SO32- (4)
fed into the reactor.
2H3O+ + 2Cl- = 2HCl + H2O (5) A drawback of this process was the limited
capacity of the limestone surface to take up
Ca2+ + SO32- + 2H2O = CaSO3 · 2H2O (6) sulphur dioxide, i.e. a layer of only about 2
It is obvious that the chloride ion works as a micrometer could built up before the stone
catalyst as it takes part in the reaction but is was saturated and had to be cleaned. One cu-
not consumed. bic meter of limestone (5 to 30 mm) would
only take up 6 kg of sulphur dioxide between
Some calcium sulphate is precipitated on the the tumbling treatments. The transport and
VGB PowerTech - Autorenexemplar - © 2011
limestone granules, therefore it is necessary to tumbling of the limestone became too exten-
circulate the stone through the bed to remove sive and too costly.
this layer.
Another problem was designing a process
where flue gas and air were to be alternatively
Development steps led through two reactors. During the exchange
of reactors, for a short time, only flue gas was
Authors In the classical wet process, limestone is fine- led into the boiler furnace with an oxygen
ly pulverised, which is emulsified in water. shortage which might cause an explosive situ-
Lars Tiberg, Ph. D.
Radscan Intervex AB The emulsion meets the flue gases containing ation.
Västeras/Sweden sulphur oxide in a scrubber tower. The reac- Our second process was designed avoiding the
tion takes place in three steps – (1) dissolution explosion risk. We called it Rotovex. A number
Mats Eriksson
Gällivare/Sweden of SO2 gas in water, (2) transport in the water of reactors were placed in a ring and a rotating
to the limestone grain and (3) reaction be- valve in the centre would lead flue gas and
LIC
01
M
Demister
Fresh limestone Quench
LIC Fresh
water
02 M
M
Sleve
M
M
Limestone 1-5 mm
Spiral dewaterer To container
M M
M
LIC
01 Fresh
water
Centrifuge
M
Buffer tank M
To water cleaning
To container
combustion air successively up and down the ring chamber towards the centre and they
through the reactors. In this way the leakage of Counter flow reactor design can flow from the ducts out in the stone bed
flue gas into the combustion chamber would and upwards towards the bed surface. As the
be rather constant never exceeding about ducts are mounted parallel to the upper conical
The advantages of counter flow processes are
10 %. This process may still be of interest for bed surface, the distance from the ducts to the
well known to chemists and physicists. The
large plants, but it has still the drawback of surface is constant over the cross section of the
incoming, most active reagents meet the out-
very big transport volumes of limestone. reactor. As a consequence, the gas velocity will
going product to be cleaned, i.e. very low con-
also be constant over the cross section of the
In our third process the heat exchange was tents of contaminants can be reached. The
reactor. The reaction zone extends from the
abandoned. We sprayed water over the bed, but outgoing reagents meet the flue gas with the
spokes up to the conical top surface.
sparsely to let the limestone dry up before it highest content of contaminants whereby the
reached the exit. The idea was to get a dry reagents will be fully used up. The limestone material is slowly transported
waste that could easily be freed from fly ash down through the reactor. The velocity is con-
Our Intervex reactor ( F i g u r e 2 ) has a coni- trolled by the exit feeder. A set of concentric
and calcium sulphite – sulphate powder. How-
cal bottom part, a cylindrical middle part and a funnels in the bottom cone under the spokes
ever, it was too difficult to avoid that wet ma-
VGB PowerTech - Autorenexemplar - © 2011
conical top. Limestone is fed from a top hop- guides the stones to make the downward flow
terial occasionally reached the outlet and
per through a central feed tube that extends velocity equal over the reactor cross section.
greatly disturbed waste treatment.
around 2 meters down in the reactor. From the The material coming out from the bottom is
Our forth process seems to be a hit. We have tube end, the stone material flows down to sieved to three fractions: the finest material <
increased the water spray to get a wet outgoing form a cone with a slide angle of around 38 1 mm goes to the waste treatment, stones 1 to
material. We introduced a quench before the degrees to the horizontal plane. The flue gas is 5 mm are taken out from the process and
limestone reactor to give an even cooling of introduced from a ring chamber around the stones > 5 mm are again transported to the top
the whole reactor. With increasing water flow, bottom end of the cylindrical middle part of the of the reactor.
we got more calcium sulphite formation in the reactor. From the ring chamber, a number of
water phase and the transport of the limestone ducts extend towards the centre of the reactor Water is spayed over the bed via a number of
through the reactor could be reduced to 10 % like spokes in a wheel. The ducts are simply nozzles that distribute the water evenly over
of what we had used earlier. F i g u r e 1 shows steel plates that are bent in an angle of around the stone bed.
a flow scheme of the process. 60 degrees with the angle upwards and they are We have tested several stainless steel grades in
open downwards. The flue gas can flow from the reactor. For the ring chamber and spokes,
15200
13000
4400
3200
Quench
37821
4000
11101
Figure 2. The Intervex reactor.
hance oxidation. Some waste limestone is in fluid. The fluid is reused as spray water. From
the form of stones < 5 mm and some in the the bottom end, a rather thick sludge is pumped
form of a fine powder. The stone is sieved to the dry fly ash container where it is used to
away and can be reused in other processes. All moisten fly ash when it is to be transported to
other wastes come as sludge. We have tested the ash deposit.
two methods to take care of it.
Figure 3. The Gällivare Intervex plant. Alternatively, the sludge is dewatered in a cen-
In one method which is used in Gällivare, we trifuge. The dry product will contain around
high alloy steels are necessary, but for the pump the sludge to a sedimentation tank. 15 % of water. The dewatered product can be
inside of the reactor, including the funnels, From the top end we take out a rather clean used in concrete production.
lower alloyed grades are sufficient.
Table 1. Technical data for intervex desulphurisation plants.
With an even gas flow upward and an even
Gällivare 20 MW peat 200 MW coal
stone flow and water flow downwards, our In-
tervex reactor gives optimum conditions for a Gas flow Nm3/s 14 92
high contaminant reduction and a high yield SO2 contents mg/Nm 3
500 1500
of the reagents. Not only sulphur, but also Fly ash contents m/Nm3g 100 150
VGB PowerTech - Autorenexemplar - © 2011
In 2009 we also made a test on completion will not need an electrostatic precipitator. A
The Gällivare plant – results when the plant was operated for 20 days with cyclone or a falling chamber will be suffi-
a strict control of the performance. The fol- cient.
lowing results were documented: The waste sludge will most often be dewatered
In 2002, we started building an Intervex plant
in Gällivare in northern Sweden for a 20 MW Flue gas flow 9 to 11 Nm /s 3 in a centrifuge instead of the sedimentation
peat-fired boiler. Gällivare is situated 100 km Contents of SO2 200 to 400 mg/Nm3 process.
north of the polar circle which means long Degree of desulphurisation 97.5 % F i g u r e 4 shows a drawing of a 13 m reactor
transports routes, long winters and sometimes (for a 160 MW coal boiler).
Availability 97.4 %
very cold weather. The reactor has a diameter We assume a reactor for a 200 MW coal-fired
Limestone yield 55 %
of 5.8 m and is designed for a flue gas flow of boiler as maximum size for one unit. It will
14 Nm3/s. At that time we used the concept Reusable
have a diameter of 15 m and a total height of
with restricted water spraying over the lime- limestone 1 to 5 mm 20 %
30 m to the top hopper.
stone reactor bed that would keep the bottom Overall limestone yield 75 %
The following advantages of the Intervex
and exit feed dry. Since then, we have intro- Since the test, Gällivare Heat and Power has process are important:
duced a quench upstream of the Intervex reac- taken over the plant. F i g u r e 3 shows a view
tor and increased water spraying to get a wet −− The reagent – limestone 5 to 30 mm – is
of the plant and Ta b l e 1 provides some cheap compared to caustic lime for the dry
waste product. We have developed the sedi- data.
mentation system for waste and the moisten- processes or the very finely ground lime-
ing system for the dry fly ash. We improved We now regard the process ready for the mar- stone of the wet process.
many components and the reactor design to ket. −− The pressure drop is lower and the electric-
eliminate the risk for clogging. In autumn ity consumption is lower than in other proc-
2009, we made the last, important improve- esses.
The final process −− The investment cost is lower than for most
ments to the reactor and since then the process
has operated according to our specifications, other processes.
although some failures occurred at external Future Intervex plants will differ from the −− High degrees of emission reduction are
components during the last year. Gällivare plant in some ways: future plants reached. □
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