Circulating fluidized beds (CFB) uses calcium based sorbents primarily limestone, for the

in-situ capture of much of the sulfur dioxide in the fuel. But it brings also some potential to
create serious operational problems and boiler maintenance issues. The recarbonation and
extended sulfation processes are just two of the dominant agglomeration and hard deposits build
up mechanism involving sorbent limestone.

RECARBONATION

Recarbonation is the reverse reaction of calcination. Opposite with that of calcination,

recarbonation occurs when (1) the partial pressure of CO 2 is higher than that of equilibrium
partial pressure of CO2 and (2) the temperature is higher than of equilibrium calcinations
temperature. But the latter has not proven true to all times since there is also recarbonation taking
place in the temperature range of 650-790 oC which is below the operating temperature of CFB.
The mechanism of recarbonation process is summarized with this reaction (1). This
reaction is an exothermic reaction.

CaO(s) + CO2 (g) = CaCO3 (s) + heat (1)

Hydration followed by recarbonation is also one of the mechanism with H2O being a
catalyst this normally occurs below temperature below 450oC.

CaO + H2O = Ca(OH)2 (2)

Ca(OH)2 + CO2 = CaCO3 + H2O (3)

EFFECT OF CO2 CONTENT

High CO2 plays a particularly important role in the recarbonation of CaO. The higher
content of CO2 corresponds to the increased conversion of CaO. CO2 and CaO are both reactants
and the higher content of CO2 leads to the adding shift of the reaction toward the product side
(CaCO3), which compensates for the imposed change in the conditions as governed by the Le
Chatelierss Principle. Example, at 90% CO2, the partial pressure of CO2 at this point is above
the dissociation pressure of CO2, so recarbonation takes place.

EFFECT OF TEMPERATURE

The effect of temperature on recarbonation was found to have a strong effect on the
conversion of CaO. Recarbonation is exothermic, which means that the forward reaction is
favored by lower temperatures (low temperature favors equilibrium conversion).
On the contrary, the conversion of CaO is significantly higher at high temperatures than
at low temperatures, when the temperature is above the equilibrium temperature. Conversion of
CaO decreases rapidly as the temperature approaches equilibrium temperature. When the
temperature is below the equilibrium temperature, the reverse reaction of recarbonation takes
place. High temperature favors the speed of reaction.

EXTENDED SULFATION
Extended sulfation is a dominant agglomeration mechanism in the systems that use high
sulfur fuel with calcium based sorbents for low ash fuels like pet coke. It occurs between
temperature ranges from 750oC to 950oC. Bed agglomeration is the process when separate bed
particles adhere to each other to form larger particles.
 The mechanism of extended sulfation process is given with this reaction (4) and (5).

CaCO3 + SO2 + O2 = CaSO4 + CO2 (4)

CaO + O2 + SO2 = CaSO4 + 486 KJ/g mol (5)

Figure 1. Consolidation mechanisms

Normally, sulfation must only occur within the circulation loop of Circulating fluidized
bed. But due to the presence of fine sorbent limestone particles which are initially calcined in the
circulation loop and that those fine particles easily escape from the cyclone, they are subjected to
extended sulfation and recarbonation resulting to sintered and hard deposits. This is also one
major reason why we need to minimize the amount of fine sorbent limestone which is less than
50 microns in order to somewhat prevent the occurrence of the said processes.

ECONOMIZER

Further if the temperature of the flue gas in vicinity of the sorbent particle is sufficiently
high, then the local temperature of the deposits is likely to exceed the sintering temperature due
to exothermic reaction and hence as a result, the agglomeration could occur.

Circulation loop

Figure 2: Recarbonation and extended sulfation range and location.

 Figure 3: Recarbonation-prone regime for limestone addition.

EFFECTS OF RECARBONATION AND EXTENDED SULFATION ON OPERATION

AND MAINTENANCE

Loose unreacted calcium oxides that settle on tubes are subjected to recarbonation and
extended sulfation resulting in hard deposits. These hard deposits were formed due to fine
calcined limestone particles (< 50 microns) that leave the cyclone. These particles settle on the
superheaters surfaces and react with CO2 between 650-750 oC leading to recarbonation and then
with SO2 between 750-850 furthering extended sulfation, forming sintered and hard deposits.
Because of the hard deposits, the superheaters and reheaters heat transfer area are being reduced.
The installment or use of high pressure soot blowers is one way of eliminating these hard
deposits but does not guarantee a complete elimination though.

Other important factors in the deposit build up were found increasing with increase in ash
content and sorbent addition.

REFERENCES:

https://www.hindawi.com/journals/jc/2013/438384/ Influence of Sorbent Characteristics

on Fouling and Deposition in Circulating Fluid Bed Boilers Firing High Sulfur Indian Lignite.

http://dc.engconfintl.org/cfb10/50/ Study of Recarbonation in Circulating Fluidized Bed

Combustion.

Beisheima, T., Ziebaa, M., & Scheffknechta, G., Experimental investigations on deposit formation
by recarbonation on external heat exchanger surfaces in oxyfuel CFB boilers.

RECARBONATION AND EXTENDED

SULFATION
 SUBMITTED TO:

ENGR. TIFFANY FAYE S. CARANTO

SUBMITTED BY:

JERIC PAUL R. CADIZ

ON-THE-JOB TRAINEE

JULY 26, 2017