J. Mater. Sci. Technol., Vol.25 No.

3, 2009 329

Effect of Reactivity of Quick Lime on the Properties
of Hydrated Lime Sorbent for SO2 Removal
H.G. Shin1)† , H. Kim1) , Y.N. Kim2) and H.S. Lee3)
1) Department of Materials Science and Engineering, Seoul National University, Seoul, Korea
2) Machinery & Materials Testing Center, Korea Testing Laboratory, Seoul, Korea
3) School of Materials Science and Engineering, Pusan National University, Busan, Korea
[Manuscript received January 16, 2008, in revised form May 16, 2008]

The hydration of quick lime and the sulfation of hydrated lime were carried out for verification of relationship
between the reactivity of quick lime and the properties of hydrated lime as a sorbent. The effect of reactivity
of quick lime was investigated with the change of calcination temperature and time. Results obtained showed
that the temperature rise during the hydration of quick limes varied from 31 to 69◦ C with the variation of
calcination temperature and time. The specific surface area and the sulfation ability of hydrated lime prepared
by hydration of quick lime showed a proportional relationship with the reactivity of quick lime. The hydrated
lime which was prepared by hydration of quick lime calcined at 1100◦ C had the highest reactivity and showed
41.53 m2 /g of the specific surface area, 0.16 cm3 /g of the pore volume and 87% of the removal efficiency for
SO2 removal.
KEY WORDS: Reactivity; Quick lime; Hydrated lime; Calcination; Hydration; Sorbent

1. Introduction a five-step mechanism[8] . Heat transfer resistances as
well as pore diffusion resistance of the CO2 evolved
might have significant effects on the calcination rate.
Limestone is one of the abundant materials in the
As it is reported by Dˇogu[9] , changes in pore struc-
world and is very useful for various applications. Both
ture also play a significant role on the calcination
quick lime and hydrated lime are produced from lime-
mechanism and the reactivity of a calcined limestone
stone by calcination and hydration. The in-duct sor-
is strongly dependent on its physical and structural
bent injection is one of the dry flue gas desulfuri-
properties which in turn are highly dependent on cal-
sation(FGD) processes. In this process, the sorbent
cination conditions[10] . However, there are many as-
particles are normally introduced into humidified and
pects not well understood about the calcination reac-
temperature-controlled flue gas in the duct between
tion, and therefore there is no consensus about several
the air pre-heater and particulate control device. The
fundamental aspects of the process as particle reaction
sorbent used widely in the humidified duct injection
model, rate-limiting processes, and total pressure on
processes is hydrated lime(Ca(OH)2 )[1] . However, the
the reaction rate etc.[11] .
sorbent is not highly converted in the operation of
In this study, the calcination of limestone with var-
these processes. How to increase the utilization of
ious temperatures, the hydration of quick lime and the
hydrated lime has been an important subject for the
sulfation of hydrated lime have been performed. It is
application of the dry processes. The superiority of
the aim of this work to relate the reactivity changes of
calcium hydroxide over calcium carbonate as a sor-
quick lime during the calcination process to the prop-
bent has been attributed to the smaller mean particle
erties of the hydrated lime in the removal of SO2 .
size, higher surface area, higher pore volume, larger
mean pore diameter, and plate-like grain structure
(as opposed to sphere-like grain structure) of CaO de- 2. Experimental
rived from Ca(OH)2 compared to that derived from
calcium carbonate. In boiler economizer and cool- Calcined quick limes were obtained in a muf-
side studies, improved SO2 removal performance has fle furnace at temperatures between 900◦ C to
been reported for calcium hydroxide. Thus, it is desir- 1200◦ C and for calcination time varying from 30 to
able to provide calcium hydroxide having high surface 180 min. Hydrated lime was achieved by hydra-
area, high porosity, and small particle size for use in tion process using water, ethanol and additive (quick
SO2 sorption, and for other physical processes relying lime:water:ethanol:additive=100 g:48 ml:72 ml:3 g).
on the sorptive capabilities of calcium hydroxide[2–5] . The resultant hydrates were dried off in an oven main-
The structural properties of the sorbents such as spe- tained at 105◦ C to produce a dry sorbents. All sam-
cific surface area and porosity are believed to play ples were then milled and sieved to a particle size
an important role in SO2 removal. In general, it below 200 µ being used in the sulfation system.
has been shown that higher desulfurization reactivity The temperature rise recorded from a room tem-
correlates with higher specific surface area[6,7] . The perature of 25◦ C during hydration was used as the
uncertainty in predicting the behavior of a particu- reactivity value of calcined quick lime[12] . The crystal
lar limestone in a calcination process is due to the structure and the crystalline size were analyzed using
complexity of the calcination process which involves a Mac Science M18XHF X-ray diffractometer (XRD).
Crystalline size was calculated from XRD data as
† Corresponding author. Prof. H.S. Lee; Tel.:+82 51 510 2388; follows[13] :
E-mail address: heesoo@pusan.ac.kr.

15405 nm for lime calcined at 900. 2009 fraction line measured at half-height of the diffraction 80 peak (in radians). B(0001) is the broadening of the (0001) dif. (c) 1000◦ C. Quick lime calcined at 1100◦ C. (d) 1100◦ C and (e) 1200◦ C . the tempera- ture rise was lower than that of quick lime calcined 3 at 1100◦ C and the time required to maximum tem- perature rise became much longer.25 No. and θ (0001) is half the diffrac- tion angle (in radians) of (0001) planes. 1.9λ surface area of quick lime as a function of calci- (1) t= B(0001) cos θ(0001) nation temperature and SEM photographs of quick where λ is the wavelength of X-rays (0. Vol. 3 SEM photographs of quick limes calcined at various temperatures: (a).. 1100 and 1200◦ C. When quick lime calcined at 1100◦ C for 1 h was hydrated. Sci. These results indicated that quick lime calcined at 1100◦ C has the 4 highest reactivity for hydration. respec- CuKα). Mater.330 J. Results and Discussion 1200 C o 0 0 300 600 900 1200 The variation of temperature rise during hydra- Time / s tion of quick limes calcined at temperature ranges of 900–1200◦ C for 1 h is shown in Fig. 1000. 1100 and 1200◦ C. In order to verify these Fig. 1000. which showed Fig. Technol. A scanning 60 electron microscope (SEM). Figures 2 and 3 show the variation of specific 0. tively. 2 900 1000 1100 1200 The reactivity of quick lime calcined at 1200◦ C seems Temp. Hitachi S-2700. The tem- Fig. / o C to decrease because of the grain growth and densifica- tion of quick lime structure. 900 C o 20 1000 C o 1100 C o 3. the specific surface areas and microstructures a function of calcination temperature of quick limes were analyzed.3. 2 Variation of specific surface area of quick limes as results. the maximum temperature rise was Specific surface area / (m /g) 69◦ C which is the highest rise among quick limes cal- 2 5 cined at 900. The specific sur- face area and the pore volume of the sorbent were C o 40 determined by nitrogen physisorption at 77 K in an T/ Autosorb-1(Quantachrome) analyser. (b) 900◦ C. was used to observe the sorbent morphology. When quick lime cal- cined at 1200◦ C for 1 h was hydrated. This means that quick lime calcined at 1200◦ C becomes less reactive. 1 Temperature rise during hydration of quick limes calcined at various temperatures perature rises accompanied by hydration of quick lime increased with calcination temperature up to 1100◦ C and decreased above the calcination temper- 6 ature.

/ 30 1200 C 1100 C o o Calcined at 20 30 min 60 min o 1100 C 10 120 min 180 min 1000 C o 0 0 500 1000 1500 2000 2500 900 C o Time / s 10 20 30 40 50 60 70 80 90 Fig. the forms of hydrates such as a paste and a powder ture for long duration time or at high temperature for as stated above. temperature are shown in Fig.2 1000◦ C 13 1100◦ C 11. Technol. 2009 331 Table 1 Crystalline sizes of hydrated limes Calcination temp.3 1200◦ C 12. The hydrated lime prepared with the quick lime hydrated lime that is produced in this process has calcined at 1100◦ C showed the lowest crystalline size high specific surface area and good handling proper. The calcination time of 120 min XRD patterns is reported in Table 1. 4 Reactivity of quick limes as a function of calcina.3 plete and partial thermal decomposition of limestone.4 2 Pore volume / (cc/g) porous. Crystals with sizes The hydration of quick lime was carried out using ranging from 11.1 60 Ca(OH) 50 CaCO 2 3 (101) (001) 40 (110) C (100) Intensity / a. The XRD patterns of hydrated limes area and reactivity of quick lime. 4.5 tion of limestone. The hydrates prepared analyzed by nitrogen adsorption measurement (BET from quick limes calcined at 900 and 1000◦ C were wet method[15] ). Figure 3(b) shows that the 20 0. Hydrated lime from are shown in Fig. calcite (CaCO3 ) cific surface area of 41. 2 / deg. Calcination temperature / o C The reactivity of quick lime calcined at 1100◦ C Fig. tion time Fig. (111) (021) o (013) (022) Temp. perature tion process. Depending on the reactivity of calcined lime. had the largest specific surface area. was found because of uncalcined CaCO3 . while the hydrates from specific surface area and the pore volume of hydrated quick limes calcined at 1100 and 1200◦ C were dried lime has a similar trend with that of specific surface powder forms. 30 while the pores on the surface of quick lime calcined at 0. a lot of pores. of hydrated limes as a function of calcination tem- The calcination time is critical during the calcina. the lime.u.3 to 13 nm appear in the hydrated water-alcohol mixture.. 0. of quick lime (Hydrated Lime) Average Crystalline size/nm 900◦ C 13. of 11.25 No. According to Oates[14] . 1200◦ C had no peaks of calcite. shown at (0001) diffraction peak. Vol. The specific sur- the form of the final products was a wet paste or a face area and the pore volume of hydrated limes were dried powder after hydration. is work. The difference showed the highest reactivity of quick lime in this of crystallinity. There were less pores on the surface of quick limes calcined at 900 and 1000◦ C because of incom. This graph shows that the variation of paste forms after hydration. J. As shown in Fig. which took place during hydration. ties. existed on the surface of particles Specific surface area (m /g) and therefore quick lime calcined at 1100◦ C was very 40 0. It is desirable that the calcination time should be as short as possible. In hydrated samples from quick quick lime calcined at 1100◦ C showed the highest spe- limes calcined at 900 and 1000◦ C. The crystalline size calculated from short duration time. Mater. It could be related to nation should be carried out either at low tempera.3 nm. which were created due to thermal decomposi. 3(d). disperses well and is far more effective in the The variation of specific surface area and the pore removal of acid gases compared to a normal hydrated volume of hydrated lime as a function of calcination lime. 5 XRD patterns of hydrated limes with variation of calcination temperature of quick limes the highest reactivity for hydration.0 after calcination. 6.1 limestone calcined at 900◦ C was not completely de- composed into quick lime and was left with quick lime 900 1000 1100 1200 0. while hy- side of CaCO3 particles and for carbon dioxide gas drated limes from quick limes calcined at 1100◦ C and to be exhausted from the inside of particles. Sci.53 m2 /g and the highest pore .3. Calci. 5. enough time must be allowed for heat to transfer to the in. 0. However.2 1200◦ C decreased because of grain growth and den- sification of quick lime. 6 Variation of specific surface area and pore volume as a function of calcination time is shown in Fig.

R15-2006-022-01001-0). 2003.H. 360. RU-11-P-15-0-000) and partially supported by grants-in- drated lime from quick lime calcined at 1200◦ C. Res. 21. 455. Teller: J.25 No. The hydrated States Patent 5492685. an aid for the National Core Research Center Program from MEST/KOSEF (No. Mohamed. The properties of hydrated lime as a sorbent International Sorbalit Symposium. hydrated lime in the removal of SO2 . Ersoy-Mericboyu. 1999. during the calcination process to the properties of the [11] F. de Diego and P. Eng. M. No. Wiley. Dahlan: Fuel. specific surface area of hydrated lime increases the re. J. 2nd tigated with the change of calcination temperature Edition. to start and proceed the hydration REFERENCES process[16] . 60.. area and the reactivity of quick lime become. Addison-Wesley. 2009 Table 2 Sulfation test results of hydrated limes Calcination temp. 3rd dition.: SO2 Control Symposium.. [8 ] O. et al. 2660. 2381.: Innovations and Uses for Lime. Am. 1972. F. 86. Kucukbayrak: Thermochim. K.D. Mater. moval efficiency for SO2 and it can be related with [5 ] Gullett. J. A. 319. 4. [6 ] N. Hydration and sulfation were carried out ¨ [10] Irfan Ar. 1998). . obtained.T. Ph... Shih and C. of the same hydration condition. Lin. the higher the specific surface 04. [15] Brunauer P.O. 1987. The [13] B. and Limestone sition of limestone are. The physical prop. [9 ] T. Dˇogu: Chem. 3. New York. Demirler and S. tion. 2006-R- limes including uncalcined limestone. The effect of reactivity of quick lime was inves.. 1978. A. [12] ASTM C110-06: Standard Test Methods for Physical ity of quick lime and the degree of thermal decompo. and Massoud Rostam-abadi: United results were reported in Table 2[17] . Karatepe.. [1 ] Z. and GUlsen Dˇ ogu: Chem. The low values of hydrated Acknowledgements limes from quick limes calcined at 900 and 1000◦ C This work was supported by the KEMCO grant were caused by low surface area and reactivity of quick funded by the Korea government (MKE.: 500◦ C SO2 Concentration : 500 ppm 1000◦ C 62 SO2 flow rate: 20 l/min Air flow rate: 200 l/min 1100◦ C 87 Pressure: 1 atm 1200◦ C 73 Sorbent : 150 g/min volume of 0.: AIChE Journal. 213. U. Wiley- results of hydration and sulfation. Chem.3.F. of SO2 removal efficiency. Liu: Ind. Lime Slaking and Factors That Affect the Process. Sessions 7-8B. 1719. and time. Song: Characterization and Application for dition in consideration of the value of reactivity and Nano-sized Lime of High Performance.. Thesis.D. 309. 2001. lime using quick lime calcined at 1100◦ C showed 87% [3 ] Schwarzkopf et al. From these results. the properties of quick lime. 1992. In case of hy. Eng. 2007. Technol. impervious layer forms on the surface of the quick lime particle making it difficult for hydration solu- tion to penetrate. 2002. 1350. 171. it is obvious that the higher the homogene. could be improved by the controlling of hydration con. S. A. This suggests that the high [4 ] Schwarzkopf et al. specific surface area of quick limes. 42.01. Vol. MA. Cullity: Elements of X-ray Diffraction. Abad. Production and Uses (Weinheim. 1991. Reading.M. Siagi.332 J..16 cm3 /g. 1996. Testing of Quick Lime. Emmet and E. Conclusions [7 ] R. [17] K. Yonsei Univ. From the results Gayan: J. Sci. Acta.B. L. Chem. VCH. The sulfation test [2 ] David Moran L. 2nd edi- close relationship between the reactivity of quick lime. 2003. R. 1981. it is clear that the main factors of hydration process are the specific sur. Lee face area and the reactivity of quick limes in the case and I. 1998. of quick lime Removal efficiency at 1 min Conditions (Hydrated Lime) /% 900◦ C 56 Reaction temp. Hydrated Lime. in order to relate the reactivity changes of quick lime 83. Sci. Garcia-Labiano. 1938. Mbarawa. 33(10). Chem. limes were affected by the reactivity and the specific [16] Mohamad Hassibi: An Overview of Lime Slaking of surface area of quick lime in the same hydration con. the specific surface area of hydrated lime and the SO2 [14] JAH Oates: in Lime and limestone: Chemistry and removal efficiency appears to be confirmed from the Technology. erties and the removal efficiency for SO2 of hydrated Soc. Levenspiel: Chemical Reaction Engineering. 131. 74.H. Eng. 57. Eng.