Progress in Energy and Combustion Science 29 (2003) 381–405

www.elsevier.com/locate/pecs

Sulfur removal at high temperature during coal combustion

in furnaces: a review
Jun Cheng*, Junhu Zhou, Jianzhong Liu, Zhijun Zhou, Zhenyu Huang,
Xinyu Cao, Xiang Zhao, Kefa Cen
Clean Energy and Environment Engineering Key Lab of Ministry of Education, Zhejiang University, Hangzhou 310027, China
Received 15 October 2002; revised 19 May 2003; accepted 19 May 2003

Abstract
This paper focuses on sulfur removal technologies in industrial grate furnaces (IGF) and pulverized coal fired boilers (PCFB)
with high flame temperature of 1200– 1600 8C. The SO2 reduction without sorbents during coal combustion, thermal stabilities
of sulfation products, kinetics of sulfur retention reactions of sorbents, desulfurization processes, and sulfur removal under
unconventional atmospheres at high temperature are reviewed. It is proposed that some powdered minerals or industrial wastes
with effective metal components may be used as sorbents for sulfur removal to promote cost effectiveness. Because the main
reason that results in low desulfurization efficiencies in IGF and PCFB is the thermal decomposition of the conventional
sulfation product CaSO4 above 1200 8C, it is key to explore new sulfation products that are thermally stable at high
temperatures. It is also necessary to study the kinetic catalysis of alkali and transitional metal compounds on sulfation reactions
under the combustion conditions of IGF and PCFB. The two-stage desulfurization process, in which SO2 is captured by sorbents
both in the coal bed and the combustion gas, is promising for IGF, especially with the humidification of flue gas in a water-film
dust catcher. The staged desulfurization process combined with air-staged combustion, in which sorbents are injected into the
primary air field and upper furnace to capture SO2 under reducing and oxidizing atmospheres, is promising for PCFB. Flue gas
recirculation is also an effective desulfurization process under O2/CO2 conditions and can give a high desulfurization efficiency
of about 80% in furnaces.
q 2003 Elsevier Ltd. All rights reserved.
Keywords: Sulfur removal; High temperatures; Coal combustion; Industrial grate furnaces; Pulverized coal fired boilers

Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 382
2. SO2 reduction without sorbents during coal combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 382
2.1. Blending coals to control the sulfur content. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 382
2.2. Self-desulfurization of coal ash during combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 383
3. Thermal stabilities of sulfation products of sorbents at high temperature . . . . . . . . . . . . . . . . . . . . . . . 385
3.1. Alkaline earth sulfates as the stable desulfurization products . . . . . . . . . . . . . . . . . . . . . . . . . . . 386
3.2. Calcium aluminate sulfate as the stable desulfurization product . . . . . . . . . . . . . . . . . . . . . . . . . 386
3.3. Calcium silicate sulfate or Fe –Si – Ca melt enwraping CaSO4 as the stable products . . . . . . . . . . 388
4. Kinetics of sulfur retention reactions of limestones at high temperature. . . . . . . . . . . . . . . . . . . . . . . . 389
4.1. Calcinations and sintering of limestones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389
4.2. Sulfation kinetics of limestones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 390
4.3. Kinetic catalysis of alkali compounds on sulfation reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . 390

* Corresponding author. Tel.: þ 86-571-879-52889; fax: þ 86-571-879-51616.

E-mail address: [email protected] (J. Cheng).

0360-1285/03/$ - see front matter q 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0360-1285(03)00030-3
382 J. Cheng et al. / Progress in Energy and Combustion Science 29 (2003) 381–405

4.4. Kinetic catalysis of transitional metal compounds on sulfation reactions . . . . . . . . . . . . . . . . . . . 390

5. Sulfur removal technologies in industrial grate furnaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391
5.1. Desulfurization processes in industrial grate furnaces. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391
5.2. Influencing factors on sulfur removal in blending sorbents with coal on grates . . . . . . . . . . . . . . 392
5.3. Influencing factors on sulfur removal in coal briquettes combustion on grates. . . . . . . . . . . . . . . 393
6. Sulfur removal technologies in pulverized coal fired boilers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 393
6.1. Desulfurization processes in pulverized coal fired boilers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 393
6.2. Activation methods in preparation of reformed sorbents. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 394
6.3. Effects of particle size on sulfur removal in the limestone injection process . . . . . . . . . . . . . . . . 394
6.4. Effects of porosity structure on sulfur removal in the limestone injection process . . . . . . . . . . . . 394
6.5. Fouling and slagging problems on hot surfaces in the sorbent injection process. . . . . . . . . . . . . . 394
6.6. Influence of sorbent injection processes on dust catching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 395
6.7. Reutilization of in-furnace desulfurization residues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 395
7. Sulfur removal under unconventional atmospheres at high temperature . . . . . . . . . . . . . . . . . . . . . . . . 396
7.1. Desulfurization under reducing and oxidizing atmospheres. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 396
7.1.1. Reducing and oxidizing atmospheres in industrial grate furnaces . . . . . . . . . . . . . . . . . . 396
7.1.2. Reducing and oxidizing atmospheres in pulverized coal fired boilers . . . . . . . . . . . . . . . 397
7.2. Desulfurization under O2/CO2 conditions by flue gas recirculation . . . . . . . . . . . . . . . . . . . . . . . 398
8. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 399
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 400
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 400

1. Introduction For sulfation phenomena in fluidized bed combustion

systems (FBC) with temperatures of about 800– 900 8C, a
Sulfur pollutants derived from coal combustion are recent comprehensive review has been given by Anthony
harmful to the environment. China is foremost in the [7] with further detailed information elsewhere [8 – 19].
world with total SO2 emissions of 23.5 million tons in
1997 [1]. 50% of this comes from power station
pulverized coal fired boilers (PCFB) and 33% from 2. SO2 reduction without sorbents during coal
industrial grate furnaces (IGF). Among the various kinds combustion
of desulfurization technologies, sulfur removal in furnaces
is competitive for controlling the SO2 pollutants derived 2.1. Blending coals to control the sulfur content
from coal combustion, due to the low capital and
operating costs. But it has met difficulties in becoming A variety of low- and high-sulfur coals from various
popular commercially, because of the initially low sources can be blended in different proportions to meet
desulfurization efficiency. The main obstacle is that the normal and optimal limits for SO2 emissions [20]. As sulfur
flame temperature in PCFB is about 1300– 1600 8C and contents are directly proportional in blending, the blend
that in IGF is about 1200– 1400 8C, which are much ratio of component coals can be determined based on sulfur
higher than the thermal stability temperature of the content to meet emission levels [21,22]. A simple goal
sulfation product CaSO4. This paper focuses on the latest programming model is developed with an objective to
development of desulfurization technologies in IGF and provide a decision support system. It determines appropriate
PCFB that solve this problem. The SO2 reduction without quantities of coal from different stockpiles for a consistent
sorbents during coal combustion, thermal stabilities of feeding of blended coal while meeting environmental and
sulfation products, kinetics of sulfur retention reactions of boiler performance requirements [23]. Although a sequence
sorbents, desulfurization processes, and sulfur removal of linear programs can give a blend ratio to achieve
under unconventional atmospheres at high temperatures the predicted sulfur content, it can not ensure a
are reviewed. The pre-combustion desulfurization good combustion or slagging performance of the blended
processes such as coal washing, liquefaction and gasifica- coal [24].
tion are beyond the present scope of discussion, as well as It is shown by experiment that some characteristic
the post-combustion desulfurization processes such as parameters of a blended coal such as ignition temperature
scrubbing flue gas with various solutions. Readers and burnout efficiency cannot be predicted from component
interested in the dry sorbent injection into the back-end coals by arithmetic averaging [25]. An overall grey
fields such as economizers or air-heaters with tempera- clustering model that takes into account the main
tures of about 200– 500 8C are referred elsewhere [2 –6]. related parameters such as ash characteristics, mineral
 J. Cheng et al. / Progress in Energy and Combustion Science 29 (2003) 381–405 383

transformation, and combustion parameters is proposed to 2.2. Self-desulfurization of coal ash during combustion
predict the slagging propensity of the blends. The results
suggest that when one coal is blended with another coal with Most organic sulfur and pyrite in coal are oxidized and
widely different reactivity or slagging potential, the slagging converted to SO2 gas during combustion in furnaces. A small
grade of the coal blends changes significantly [26]. part of the sulfur may be retained as solid compounds, due to
The mineral transformation during coal blends combustion the contribution of alkaline components such as CaO, MgO,
is affected by both the mineral species interaction and the Al2O3, Fe2O3, K2O, Na2O in coal ash. The alkaline sulfates
combustion behavior. Some combinations of component are dominant at lower temperatures under oxidizing
coal’s mineral produce low-melting eutectic minerals at conditions, whereas most of them are sulfides under
high temperature and this is the main reason causing the reducing conditions [36]. It is necessary for boiler operators
non-arithmetic averaging of ash fusion temperature of to evaluate the conversion percentage of feed sulfur into
blends [27,28]. A back-propagation (BP) neural network is gaseous pollutants and select a proper desulfurization
introduced into this coal blending optimization to accurately process to meet the Clean Air Act. The desulfurization
predict some non-linear coal properties such as ash fusion property of coal ash during combustion is mainly affected by
temperature. Compared to the traditional techniques such as the boiler shape, flame temperature, residence time in the
the ternary equilibrium phase diagrams and regression furnace, initial molar ratio of Ca/S and reaction activity of
relationships, the modeling process in the BP networks is alkaline components.
much more convenient and direct, for there is no necessity to With a suitable furnace temperature of about
specify a mathematical relationship between the input and 800–900 8C, a long residence time of particles and a good
output variables. Moreover, the trained BP model can gas– solid contact condition, a FBC gives a higher self-
always achieve much better prediction results than desulfurization efficiency than a IGF or PCFB even for the
traditional methods [29,30]. As a complex regression same coal. Due to the high flame temperature of about
method in nature, the model can give rather precise 1300–1600 8C and short residence time of about 1 – 2 s,
prediction for the trained coal samples, but less for the coal ash generally gives a desulfurization efficiency of lower
new samples. than 25% in a PCFB [37]. It is indicated that about 70% of
A Coal Quality Expert system has been developed by feed sulfur is turned into SO2 gas, less than 10% is retained
ABB/CE company for controlling coal cleaning or blending in the fly ash and less than 1% is held in the bottom ash.
to provide clean coal products [31]. Based on a non-linear On the other hand, about 60% of feed calcium is retained in
programming model, a coal blending expert system is the fly ash and less than 10% is found in the bottom ash.
developed to realize the multi-target optimization. The XRD pattern of fly ash derived from Shenmu coal
The characteristic parameters such as heating value, volatile combustion in a 1000 t/h PCFB is shown in Fig. 1. It is
matter, ash content, sulfur content, ash fusion temperature, obtained by calculation that the content of glassy non-
ignition temperature and burnout efficiency are taken into crystal phase is about 70%, the content of self-desulfuriza-
account in the system. In accordance with the actual blend tion product CaSO4 phase is 3.4%, and the content of
production process, the mixed discrete-variable remained active CaCO3 and CaO phases are, respectively,
optimization design algorithm is employed to solve the 4.7 and 2.2%. However, the content of melted non-crystal
coal-blending project, which is based on BP neural network phase is only about 26% and no CaSO4 phase is detected in
models for some complex quality parameters of blends. the bottom ash [38]. It is pointed out that calcium plays a
Application of this novel coal blending technology indicates dominant role in sulfur retention of laboratory-prepared ash,
that it is much more useful and reasonable to guide blend while the contributions of other elements are limited. But in
production than the traditional methods [32 –34]. In order to a PCFB, the contribution of calcium is reduced markedly,
obtain an optimum blend ratio, a reasonable ratio index of while the roles of other alkaline elements are enhanced [37].
price to quality also can be introduced, simultaneously In my opinion, this statement is questionable. It is difficult
considering the influences of heating value, volatile matter, for the sulfates of other minor elements, such as MgSO4,
ash content and sulfur content [35]. Al2(SO4)3, Fe2(SO4)3, K2SO4, Na2SO4 which are less
As a viable cost-effective alternative to comply with thermally stable than CaSO4, to act as the sulfation
environmental considerations, power coal blending process products during coal combustion at high temperature.
has been considered extensively. But it is subject to error Furthermore, it is found by X-ray powder diffraction
and insufficient to consider only the sulfur pollutant (XRD) analysis that the CaSO4 phase is the main sulfation
emissions in coal blending, ignoring the changes in product retained in fly ash for a PCFB, and generally no
combustion and slagging performances. Also, due to the sulfates of other elements are detected. Therefore, calcium
restrictions of component coals, it is difficult to realize should play a dominant role in sulfur retention of coal ash
the optimization in each parameter of a blended coal. A not only in the laboratory but also in a PCFB.
case-by-case evaluation must be made in order to determine The higher the steam load or flame temperature, the
whether limitations imposed by blending coals are lower desulfurization efficiency is. It is reported that the
acceptable to the user’s situations. self-desulfurization efficiency of Shenmu coal sharply
384 J. Cheng et al. / Progress in Energy and Combustion Science 29 (2003) 381–405

Fig. 1. XRD pattern of fly ash derived from coal combustion in a 1000 t/h PCFB.

decreases from 63 to 6% in a tubular furnace, with an ash prepared at 1200 8C, because of their complete
increase in furnace temperature from 800 to 1200 8C. decomposition, as shown in Fig. 2. Most of the free calcium
According to XRD analysis, the content of sulfation product ions Ca2þ in raw coal ash are converted into a part of the
CaSO4 phase reaches 18% in Shenmu coal ash prepared at melted glassy matter and entirely lose their activity [38].
800 8C, while the total content of remaining CaCO3 and A general trend can be found that the sulfur retention
CaO phases is 22%. Neither active CaCO3 and CaO phases efficiency of coal ash is promoted by an increase in molar
nor sulfation product CaSO4 phase remain in Shenmu coal ratio of Ca/S, as shown in Fig. 3 [37,39,40]. However, there

Fig. 2. XRD pattern of Shenmu coal ash prepared at 1200 8C.

 J. Cheng et al. / Progress in Energy and Combustion Science 29 (2003) 381–405 385

Fig. 3. Correlation of sulfur retention by coal ash with initial Ca/S molar ratio.

is some scattering in regression of sulfur retention of ash, and so is the calcium that has the ability for sulfur
lab-prepared coal ash against Ca/S molar ratio, resulting retention. To explain this non-balance needs further research.
from that the calcium amount involved in sulfur capture
reaction is different as different coal is ashed and other
alkaline elements in coal may also have made contributions 3. Thermal stabilities of sulfation products
to sulfur retention. The transformations of alkaline of sorbents at high temperature
components in a PCFB are different from those in lab
ashing process, mainly due to high combustion temperature The desulfurization capabilities of limestones are
and short residence time of particles. For example, the ratio strongly affected by thermal conditions, especially the
of Ca/S in Shenmu coal (sulfur content ¼ 0.6%), Huangling furnace temperature. The calcium-based sorbents can only
coal (sulfur content ¼ 1.1%) and Changguang coal give low sulfur removal efficiencies during coal combustion
(sulfur content ¼ 4.3%) is, respectively, 1.5, 1.1 and 0.3. in IGF with the flame temperature of 1200– 1400 8C or in
In a lab-scale tubular furnace, Shenmu coal achieves a sulfur PCFB of 1300– 1600 8C, that are much lower than in FBC of
self-retention efficiency of 23.8% at 1100 8C, which is much 850– 900 8C. The key problem that controls the sulfur
higher than that of Huangling coal (13.3%) and Changguang removal efficiency is the thermal instability of the conven-
coal (13.7%) [38]. For Shikantai coal with a high molar ratio tional sulfation product CaSO4 above 1200 8C. In order to
of 4.0, a self-desulfurization efficiency of 28.4% is obtained develop highly effective sorbents suitable for sulfur removal
in a lab-scale PCFB [41]. The self-desulfurization efficiency at high temperatures, which is of interest to boiler operators,
of Shenmu coal reaches 27 –33% in a 1000 t/h PCFB [38]. how to form thermally stable sulfation products is an
It is valuable to further investigate the thermal behaviors important issue. From the point of view of chemical
of minor elements in coal ash and their affinities for sulfur thermodynamics, strontium sulfate (SrSO4), barium sulfate
during coal combustion. In a full-scale experiment, it is (BaSO4), calcium aluminosulfate (3CaO·3Al2O3·CaSO4)
difficult to obtain a mass balance between the feed sulfur in and calcium silicate sulfate (Ca5(SiO4)2SO4) may act as
coal and the discharge sulfur in flue gas, fly ash and bottom thermally stable sulfation products at high temperatures as
386 J. Cheng et al. / Progress in Energy and Combustion Science 29 (2003) 381–405

well as CaSO4 and CaS, although these also have some that the CaS phase is the main sulfation product and retains a
defects for sulfur removal during coal combustion which sulfur content of 4.7% in a desulfurization residue obtained
needs further examination. at 1300 8C. This is higher than the sulfur content of 1.8% in
raw coal ash [46]. Because there exist local reducing regions
3.1. Alkaline earth sulfates as the stable desulfurization under otherwise total oxidizing conditions in industrial
products furnaces, it is possible to make use of the temperature
and atmosphere distribution to produce CaS or a-CaSO4 as
Magnesium, calcium, strontium and barium all belong to sulfation products, which can promote SO2 reduction from
the alkaline earth metal group. Consequently, they have the flue gas in IGF or PCFB.
similar chemical and physical properties, including the If SrCO3 or Sr(OH)2 is used as sorbents to capture SO2
sulfur retention capability. The thermal stabilities of gas during coal combustion, SrSO4 that is thermally stable
alkaline earth carbonates and sulfates gradually increase to temperatures up to 1580 8C will act as the sulfation
from magnesium to barium. Because MgSO4 completely product. Because the atomic weight of Sr is 2.2 times that of
decomposes at about 750 8C when carbon exists, it is not Ca, strontium compounds are much heavier and more
suitable to act as the sulfation product under combustion expensive than the corresponding calcium compounds with
conditions in IGF or PCFB. the same molar ratio to sulfur. It is still better to prepare new
It is well known that CaCO3 that rapidly decomposes at sorbents composed of large amount of limestone and a little
about 800 8C is often used as sorbent to capture SO2 to of SrCO3. It is shown by experiments that SrCO3 can
produce CaSO4. It is shown by experiment that the promote the sulfur removal efficiency of limestone [47].
decomposition percentage of CaSO4 increases with the When 0.2 wt% SrCO3 and 8 wt% CaO are added into the
increasing furnace temperature. It scarcely decomposes coal, a sulfation product SrSO4 phase is detected in
below 1050 8C and only gives a decomposition percentage the combustion residue [48]. How to take effective measures
of 13 wt% at 1150 8C. But the decomposition percentage to enhance the yield of the thermally stable SrSO4 during
dramatically increases to 57 wt% at 1200 8C and 96 wt% at coal combustion needs further research.
1300 8C, which indicates that 1200 8C is the turning point of Because BaCO3 rapidly decomposes at about 1300 8C
the decomposition of CaSO4 [38]. It is known that the and BaSO4 is more thermally stable than SrSO4, it is
decomposition of CaSO4 is accelerated in a reducing possible to use BaCO3 as a sorbent for sulfur removal to
atmosphere or at carbon surfaces. With some obtain the sulfation product BaSO4 at high temperatures.
impurities such as NaCl, SiO2 or steam, the initial As shown in Fig. 4, adding BaCO3 with a molar ratio of Ba/
decomposition temperature of CaSO4 decreases, while the S at 2 gives a high sulfur removal efficiency of 44.5% during
decomposition rate increases. The traditional limestone, coal combustion at 1250 8C in a tubular furnace. It is higher
Ca(OH)2, dolomite and dolomitic hydrate, respectively, than the low sulfur removal efficiency of 10.6% when
give desulfurization efficiencies of 30 –45, 40 – 60, 40 – 60 CaCO3 is added into the coal with a molar ratio of Ca/S at 2.
and 50 – 65% in a furnace injection process [42]. The reason But due to the higher atomic weight of Ba, which is 3.4
why dolomite gives a higher desulfurization efficiency times that of Ca, it is more practical to blend expensive
than limestone is that inert MgO crystals disperse the barium compounds with limestones for sulfur removal. It is
smaller CaO crystals, which leads to a higher porosity in shown by experiments that barium ion Ba2þ has better
calcined dolomite during the sulfation procedure [43]. desulfurization capability than calcium ion Ca2þ at high
It should be noted that CaSO4 has three allotropes that temperatures of 1200–1300 8C, while carbonate radicle
2
have different structures and chemical properties. CO223 excels hydroxide radicle OH . When BaCO3 content
The metastable and soluble g-CaSO4 is derived from the decreases and CaCO3 content increases, the sulfur removal
dehydration of CaSO4·2H2O at 130– 200 8C. b-CaSO4 is efficiency of sorbents gradually declines, with a constant
produced from g-CaSO4 at 300 8C. The a-CaSO4 obtained sum of molar ratios of Ba/S and Ca/S at 2, as shown in Fig. 5
at high temperature is thermally stable from 1210 8C up to [38]. There is still much to do to reform the composition and
its melting point of 1495 8C [44]. However, which kind of preparation of barium-based sorbents for more effective
CaSO4 formed during coal combustion and how to promote sulfur removal.
the yield of a-CaSO4 are interesting subjects and need
further research. In a normal Ca –S– O reaction system, 3.2. Calcium aluminate sulfate as the stable
CaS that is thermally stable at high temperature up to desulfurization product
2400 8C in reducing atmospheres [45] can also act as the
sulfur retention product, besides CaSO4. CaS can be In terms of powder diffraction files published by JCPDS
produced from the reaction of CaO with H2S gas in a [49,50], calcium aluminate sulfate (3CaO·3Al2O3·CaSO4) is
reducing atmosphere, or from the reaction of CaSO4 with a ternary compound. It is the main constituent in
carbon at coal particle surfaces. When CaO and some sulfo-aluminous clinker, which is used as an expansive
additives are added into coal briquette at Ca/S ¼ 2, it is agent in manufacturing expansive cement. It is synthesized
found by XRD and X-ray fluorescence analysis (XRFA) by heating a mixture of lime, alumina and CaSO4 at
 J. Cheng et al. / Progress in Energy and Combustion Science 29 (2003) 381–405 387

Fig. 4. Desulfurization with barium compounds during coal combustion.

1350 8C. As calcium aluminate sulfate has better thermal combustion, as shown in Fig. 6. To a certain extent, the finer
stability than CaSO4, the possibility for the ternary reactant particles and longer reaction time, the more
compound to act as the sulfation product during coal 3CaO·3Al2O3·CaSO4 is formed and less SO2 pollutant is
combustion has been examined by various authors. emitted [51]. Although a mixture composed of pure CaO,
The crystal phase 3CaO·3Al2O3·CaSO4 is detected in Al2O3 and CaSO4 with the molar ratio of 3:3:1 gives a high
the desulfurization residue derived from coal briquette sulfur retention efficiency at about 1300 8C, an additive

Fig. 5. Desulfurization with BaCO3 and CaCO3 during coal combustion.

388 J. Cheng et al. / Progress in Energy and Combustion Science 29 (2003) 381–405

Fig. 6. XRD pattern of desulfurization residue derived from coal combustion.

composed of CaO and Al2O3 gives only a low SO2 reduction Ca5(SiO4)2SO4 is more thermally stable and can act as a
from the flue gas during coal combustion [52]. This is sulfation product during coal combustion at high
mainly because of the other ensuing mechanisms that inhibit temperatures. However, the formation mechanisms of
the formation of calcium aluminate sulfate. Therefore, how Ca 5 (SiO 4 ) 2 SO 4 during coal combustion, the reaction
to enhance the yield of 3CaO·3Al2O3·CaSO4 during coal schemes, conditions, extents and rates, are far from clear.
combustion is a key problem, that still has many difficulties Unfortunately, the contribution of Ca5(SiO4)2SO4 to
to overcome in practice. retain sulfur during coal combustion at high temperatures
is uncertain. Most authors have paid attention to the Fe –
3.3. Calcium silicate sulfate or Fe – Si– Ca melt enwraping Si– Ca melt that physically enwraps the sulfation product
CaSO4 as the stable products CaSO4 so preventing its thermal decomposition. It is found
that simultaneously adding Fe2O3 and SiO2 into CaO can
The high-temperature phase equilibrium in CaO– SiO2 – promote the sulfur retention efficiency from 46 to 65%
SO3 system is important in the chemistry of during coal combustion at 1200 8C. This results from
traditional cements. Calcium silicate sulfate Ca5(SiO4)2SO4 the formation of a new heat-resisting crystal phase
(from a very reliable JCPDS file: 26-1071) [44] and calcium CaFe 3 (SiO 4 ) 2 OH which enwraps the sulfation product
silicosulfate 2Ca2SiO4·CaSO4 (from an uncertain JCPDS CaSO 4 [55]. Because of its crystal structure, CaSO4 does
file: 18-307) [49] are interesting allotropes. It is pointed out not form a solid solution with silicates at high temperatures,
that Ca5(SiO4)2SO4 is synthesized from siliceous lime sand, but is enwrapped by silicates melt. Some individual phases
which contains 83 wt% CaCO3 and 13 wt% SiO2, with SO3 such as CaSO4, 2Al2O3·3SiO2 and a-Fe2O3 are found by
which is produced in the air-blast injection of fuel-oil with XRD analysis in the desulfurization residue derived from
3.8% sulfur content. It forms in the flame area between coal combustion, but no new sulfation compound containing
the refractory lining (30% Al2O3 brick) and an outer layer silicon and ferrum is detected. It is shown by scanning
of larnite in a lime kiln, with a flame temperature of electron microscope (SEM) and energy dispersive X-ray
1500– 1600 8C and a kiln-wall coating temperature of about analysis (EDAX) that silicates with Si and Fe contents
1100 8C [53]. 2Ca2SiO4·CaSO4 is prepared from calcium closely enwrap CaSO4 and prevent it from decomposing at
carbonate, crushed quartz and AnalaR CaSO4·2H2O which high temperatures [56,57]. Which is the main sulfation
are finely ground to pass a 300-mesh sieve, by ignition at product of silicates, the Fe – Si– Ca melt enwraping CaSO4
1150 8C for 150 h in a platinum –rhodium resistance furnace or calcium silicate sulfate Ca5(SiO4)2SO4? It is still
[54]. Compared to 2Ca2SiO4·CaSO4, calcium silicate sulfate unknown. The former is mainly formed through a physical
 J. Cheng et al. / Progress in Energy and Combustion Science 29 (2003) 381–405 389

flow and enwrapping process, while the latter is mainly The calcination mechanisms of limestones vary with
formed through a chemical combination process. particle diameters and furnace temperatures. In the
Because the high-temperature behavior of silicates during calcination procedure of limestones with particle diam-
coal combustion is complicated and the identification of eters of 9 –16 mm, the rate-controlling step is chemical
complex desulfurization phases needs advanced analysis reaction that follows the single-step nucleating mechan-
techniques, it is a challenge to clarify the reaction ism [61]. The decomposition of limestone with the
mechanisms. particle diameter of about 14 mm is mainly controlled by
The above discussions are based on the viewpoint that chemical reaction at 1000 8C, while the decomposition of
silicon compounds are beneficial to SO2 reduction from the limestone with the particle diameter of about 91 mm at
flue gas. On the other hand, it should be noted that SiO2 1100 8C and that with the particle diameter of about
cannot only form silicates that enwrap the sulfation product 152 mm at 1200 8C is mainly controlled by CO2 gas
CaSO4, but also form a CaO – SiO2 phase that has a low diffusion [62]. It is assumed by a reformed partly
capacity for sulfur retention. The formation conditions of sintered globe model that calcination follows one class
calcium silicate sulfate and Fe – Si – Ca melt enwraping of reaction dynamics in a furnace sorbent injection (FSI)
CaSO4 are also not clear and affected by the variable process [63]. A number of efforts have been made to try
combustion conditions. Hence, adding silicon compounds to produce calcinated limestones with large surface areas.
into the fired coal sometimes may be harmful to sulfur The fragmentation behavior is a function of sorbent type,
removal under certain conditions. Whether the Fe – Si – Ca particle size and particle temperatures in the range of
sorbents are beneficial or harmful during coal combustion 600–1600 8C, with the sorbent type being the dominant
depend upon factors such as heating rate, furnace parameter. It is found that dolostone is more susceptible
temperature and reaction activity of the silicates. It is to breakage than limestone [64], and the decomposition
reported that simultaneously adding Fe2O3 and SiO2 into of calcium hydroxide produces larger CaO surface area
CaCO3 with the same weight ratio of 0.1% promotes the than calcination of limestone [65,66]. Calcining different
sulfur removal efficiency from 41.2 to 53.8% at a constant limestones under the same conditions yields different
heating rate from room temperature to 1080 8C, while surface areas and porosities [67,68]. Even for the same
decreases the efficiency at a constant furnace temperature of limestone, the surface area varies with the calcining
1080 8C [58]. When Na2SiO3·9H2O is added into CaCO3 conditions such as furnace temperature, duration and
with a weight ratio of 0.6%, the sulfur removal efficiency is particle diameter. It is reported that the surface area of
promoted from 16 to 33% at 1200 8C. But when the furnace limestone firstly increases due to calcination and then
temperature is lower than 1100 8C, the sulfur removal decreases due to sintering, with increasing duration at the
efficiency is decreased [59]. It is found that a kind of clay temperatures of 900– 1100 8C. The calcined limestone
mineral can promote the desulfurization efficiency of obtains a maximum surface area of 47 m2/g at 1100 8C,
CaCO3 from 16 to 31% during coal combustion at which is higher than that of 27 m2/g at 900 8C [62].
1200 8C, but other clay minerals such as bentonite and The surface area of calcined limestone depends on the
zeolite have little promotion effects for sulfur removal [60]. calcination rate and sintering rate [69]. The sintering of
Because the silicon compounds as inert mineral ingredients calcined limestone results in a decrease in surface area and
are harmful to coal combustion and promote the sulfur porosity, which leads to compact crystals with much lower
removal in a limited range, it is not wise to add extra silicon reaction activities [70]. The sintering characteristics of
compounds into the fired coal. There are large amount of limestones are strongly affected by furnace temperature,
silicon ingredients in coal ash, which can take part in the residence time and reaction atmosphere, in which
desulfurization reactions during coal combustion. It is useful temperature is the most important factor. In general,
to study how to activate these silicon ingredients to form sintering rate accelerates with an increase in temperature.
thermally stable sulfation products for effective sulfur But the rate increases slowly below the critical Tamman
removal in furnaces. temperature which is 0.4 – 0.5 times the melting temperature
of solid, and increases rapidly above it. For CaO crystal
whose melting temperature is 2500 8C, the Tamman
temperature is about 1000 – 1250 8C. It is shown by
4. Kinetics of sulfur retention reactions
experiment that the surface area of calcined limestone
of limestones at high temperature
decreases sharply due to the increased sintering above
1100 8C [71]. Prolonged residence time also gives an
4.1. Calcinations and sintering of limestones increase in sintering rate, especially when the temperature
is above 1000 8C. It is reported that the sintering extent of
The porosity structures of calcined limestones are CaO particles with diameters of 0.1 – 0.3 mm is enhanced
important for the high-temperature and short-time sulfa- by an increase in temperature and duration [72].
tion reactions in furnaces, thus it is important to study The atmosphere and impurities also have important effects
the calcinations and sintering performance of limestones. on sintering properties of limestones. It is found that SO2
390 J. Cheng et al. / Progress in Energy and Combustion Science 29 (2003) 381–405

and CO2 gases strengthen the sintering effects, as do The sulfation reactions are affected by many operational
impurities such as Fe2O3, Al2O3 and SiO2 in the parent factors, such as furnace temperature, residence time, SO2
limestones [73]. In a limestone injection process, the partial pressure and molar ratio Ca/S. Also, the limestones
presence of CO2, SO2, O2 or CO compositions in the flue from different sources have different calcination and
gas produces various degrees of sintering of CaO particles. sulfation performances. It is reported that Changshan
Extensive sintering occurs with CO2 compositions. When limestone has a better sulfur removal capability than
O2 and SO2 gases exist in the flue gas, sintering of the dust is Jiawang limestone or Tongshan limestone under the same
reduced with a higher initial content of the sulfation conditions, due to the smaller particle diameter and larger
product CaSO4. With CO gas in the flue gas, the contrary surface area resulted from calcination and impurities [79].
is found [74].
4.3. Kinetic catalysis of alkali compounds
4.2. Sulfation kinetics of limestones on sulfation reactions

The mechanisms of high-temperature and short-time It is known that adding alkali compounds such as
sulfation reactions in a limestone injection process can be NaCl into limestones can promote the sulfur removal
well characterized by a two-stage process with a very fast efficiency during coal combustion. It is reported that the
initial surface reaction and followed by a product layer conversion percentage of CaO, which contains NaCl up
diffusion controlled step for CaO – SO2 reaction. to 3 wt%, first increases to 26 wt% and then drops to
The reaction rate is very rapid and about 45% removal is 18 wt%, whilst the conversion percentage of raw CaO is
reached during the first 0.3 s. The reaction then 20 wt% at 850 8C. Maximum conversion percentage is
declines markedly, but a residence time of 2 s is still obtained when the NaCl content is about 2 wt% [80 – 82].
necessary to obtain a reasonable SO2 reduction [43,75]. In general, the sodium compounds readily vaporize under
Although calcination increases surface area and utilization combustion temperatures. The reaction of CaO with
of sorbents, an unreacted nucleus usually remains in the sodium induces particle fragmentation and large cracks,
partly sulfated CaO particle under furnace injection which increases the number of CaO sites that are readily
conditions. This is attributed to plugging of intraparticle available. In addition, a sufficient concentration of
pores and enveloping of particles by the product CaSO4. sodium impregnated in CaO produces a thin surface
Chemical reaction is a rate-limiting step only in the early eutectic layer made up of NaCl/CaO that is highly active.
stage when a continuous product layer has not been formed. The presence of the liquid phase increases the diffusion
For the bulk of the reaction when the product layer diffusion of SO2 in the product layer to inner unreacted CaO that
is a rate-determining step, it is important to understand how is inaccessible in the solid phase, and therefore promotes
and where the solid and gaseous reactants interact. the overall conversion [83,84].
One opinion is that SO2 and O2 penetrate inwards through In my opinion, alkali compounds mainly have a catalysis
the product layer by gaseous or solid state diffusion, meeting effect on sulfation reactions below 1200 8C, where the
CaO at the interface between CaO and CaSO4 where dynamic rate is the determining factor for sulfur removal.
sulfation takes place. This reaction mode has been assumed When the furnace temperature is higher than 1200 8C,
whenever the untreated core model or the grain model is the thermal stability of the sulfation products becomes the
applied. Another opinion is that the solid reactant migrates controlling factor, while the dynamic rate is secondary.
outwards through the product layer by ionic diffusion, Therefore, simply blending alkali compounds into the fired
meeting SO2 and O2 at the outer surface of the CaSO4 coal probably gives little promotion for sulfur removal at
product layer where reaction occurs. Evidence to support the high temperatures in IGF and PCFB.
latter mechanism is from sulfation reactions at 1300 8C.
A combination of the two mechanisms is also possible, 4.4. Kinetic catalysis of transitional metal compounds
that is chemical reactions may occur at both locations. on sulfation reactions
Accepting the assumption that chemical reactions take place
at the interface of the reactant and product layer, a Transitional metal compounds such as FeCl3 and Cr2O3
crystallization and fracture model is developed based on can also accelerate CaO sulfation reactions during coal
free energy-work analysis. It is found that the product combustion. FeCl3 acts as both a catalyst and an absorbent
‘layer’ formed in the early stage of the reaction is not a true in conversion of sulfur in coal to SO2. Due to the catalysis of
layer, but isolated nuclei and crystals. The ‘continuous’ FeCl3, the activation energy required for SO2 formation is
product layer formed in the later stage is a monolayer of reduced. This results in that the two peak temperatures of
individual crystals with pore size of 2 – 3 nm along the sulfur emission are both reduced and their interval is
boundaries. The product layer is more porous when enlarged. Meanwhile, the first sulfur emission peak derived
developed from larger stable nuclei formed during the from coal combustion with FeCl3 is higher than that without
initial reaction at higher temperature and lower SO2 sorbent. However, due to the subsequent absorption effect of
concentration [76 – 78]. FeCl3, the second sulfur emission peak is dramatically
 J. Cheng et al. / Progress in Energy and Combustion Science 29 (2003) 381–405 391

Fig. 7. Effect of FeCl3 on SO2 emission from coal combustion.

decreased, as shown in Fig. 7 [85,86]. Cr2O3 can promote CaCO3 is added into coal briquette [89]. In recent years,
the sulfation rate of CaO because of the rapid diffusion of biobriquettes prepared from coal and biomass under high
SO2 into unreacted CaO sites through a liquid low-melting compression have been developed for clean coal
eutectic phase resulted from the reaction of Cr2O3 with CaO combustion in small boilers and stoves. The desulfurization
above 1000 8C [83]. Just like alkali compounds, transitional efficiency of biobriquettes is strongly affected by coal type
metal compounds mainly exhibit their catalysis effects on and it varies in the range 25 – 67% for eight experimental
sulfation reactions below 1200 8C, where the dynamic rate is coals [90].
the determining factor for sulfur removal. For conventional grate furnaces, the combustion con-
ditions in the coal bed are not conducive to efficient sulfur
capture. More suitable conditions for sulfur capture exist
immediately above the coal bed, where combustion gas
5. Sulfur removal technologies in industrial grate
temperature is below 1200 8C. Injecting sorbents into the
furnaces
combustion gas gives higher sulfur removal efficiency rather
than blending sorbents with coal on the grate [91].
5.1. Desulfurization processes in industrial grate furnaces Sorbent injection processes for SO2 removal are available
and in continuing development. They are generally
Simply blending limestones with feed coal at Ca/S ¼ 2 characterized by low capital cost and modest SO2 removal
only gives a low sulfur removal efficiency of 15 – 20% efficiency of 40 – 60%. The limestone injection process can
during coal combustion on grates, which cannot meet the give SO2 removal efficiency about 37% in a 20 t/h traveling
current requirements of SO2 emissions [45,87]. This is grate furnace [92]. The efficiency of 65% can also be
mainly because of the thermal instability of sulfation obtained by a sorbent injection process in a 24 MW
products above 1200 8C and the long duration about 1 h in traveling grate furnace [93].
the coal bed. Also, the short residence time of SO2/H2S gas As we know, the thermal conditions have great
in the coal bed, which is less than 1 s, cannot be ignored influences on SO2 reduction during coal combustion. It is
as well as the poor contact between the gases and powder reported that blending CaO with feed coal or injecting it
sorbents. directly into the combustion gas only gives a sulfur
Coal briquettes have been shown to be effective for removal efficiency of 26.6 and 56.7%, respectively, [94].
sulfur retention during combustion on grates. An industrial A two-stage desulfurization approach that combines
briquette prepared from 87 wt% hardcoal, 7 wt% molasses blending and injecting processes is proposed, as shown in
pulp and 6 wt% hydration limestone gives an effective SO2 Fig. 8. It promotes the sulfur removal efficiency to about
reduction in a 46.5 MW traveling grate furnace [88]. It is 75% during coal combustion, because SO2 can be both fixed
reported that a SO2 reduction of 40% from the flue gas is by the blended sorbents in coal bed and captured by the
obtained in a 4 t/h traveling grate furnace when reformed injected sorbents in combustion gas [94,95]. Applying
392 J. Cheng et al. / Progress in Energy and Combustion Science 29 (2003) 381–405

Fig. 8. Schematic of a two-stage desulfurization process in a traveling grate furnace.

the two-stage desulfurization process to a 10 t/h traveling gas derived from the oxidization of pyrite at 700– 800 8C,
grate furnace gives an in-furnace SO2 reduction of 75 – 77% but it hardly capture the SO2 gas released at lower
and a total SO2 reduction of 85 – 90% after flue gas temperature. As shown in Fig. 9, a mixture of calcium
humidification in a water-film dust catcher [96,97]. carbide residue and limestone with a weight ratio of 40:60
gives a good sulfur removal efficiency of 46% at the furnace
5.2. Influencing factors on sulfur removal in blending temperature of 1200 8C, which is much better than that of
sorbents with coal on grates any component [22,96]. When sorbents composed of
industrial wastes are added into the fired coal, a sulfur
The added quantity, particle size and composition of removal efficiency of 40% is obtained in a 6 t/h traveling
calcium-based sorbents only have certain effects on grate furnace [103]. By XRD analysis, the thermally stable
the sulfur removal during coal combustion on grates. The
ideal molar ratio of Ca/S is two and its further increase has
little benefit. For example, when the molar ratio of Ca/S
increases from 2 to 6, calcium carbide residue gives little
promotion in sulfur removal efficiency from 23 to 24% [94].
When coarse limestones with particle diameters of 1 – 3 mm
are blended with feed coal at Ca/S ¼ 2, a SO2 reduction in
the flue gas about 24% is obtained. Even finer limestones
only give sulfur removal efficiency about 30% [98– 101].
When sorbent particle size decreases from 75 to 0.1 mm, the
sulfur removal efficiency increases in a narrow range of 6%
[94]. It is favorable to prepare effective sorbents according
to the nature of the sulfur in coal [102]. Calcium carbide
residue as an industrial waste is mainly composed of
Ca(OH)2. It can effectively capture SO2 gas derived from
the oxidization of organic sulfur at 400– 500 8C, but is apt to
undergo severe sintering at higher temperature. A limestone Fig. 9. Effects of calcium-based sorbents on sulfur release during
mainly composed of CaCO3 can effectively capture the SO2 coal combustion.
 J. Cheng et al. / Progress in Energy and Combustion Science 29 (2003) 381–405 393

a short residual lifespan, the potential for application

depends on practical factors in plants.

6. Sulfur removal technologies in pulverized

coal fired boilers

6.1. Desulfurization processes in pulverized

coal fired boilers

Sorbent injection locations are critical for sulfur removal

from flue gas in PCFB. In order to determine the optimal
injection location that leads to the highest desulfurization
efficiency, it is essential to perform calculations based on
Fig. 10. XRD analysis of desulfurization residue derived from coal calcination – sulfation models for the actual industrial
combustion on grates. conditions [108]. Several desulfurization processes have
been developed and demonstrated in experimental or
phases of CaSO 4 , CaS, 3CaO·3Al 2 O 3 ·CaSO 4 and industrial PCFBs. A limestone injection multi-stage burner
Ca 5 (SiO 4 ) 2 SO 4 are found in desulfurization residue process (LIMB) in which limestone is added to the periphery
derived from coal combustion on grates, as shown in of a ‘Low NOx’ burner typically reduces SO2 emissions by
Fig. 10. How to promote the yield of the thermally stable 30– 50% at Ca/S ¼ 2 [45,109]. An upper-FSI process gives
sulfation products is a key problem in resolving the low a SO2 reduction of 30 – 40% at Ca/S ¼ 2 [110]. It is reported
desulfurization efficiency on grates [94]. that injecting limestone into a 10 t/h corner-tube furnace
gives an in-furnace SO2 reduction of 33% and a total
SO2 reduction of 60% after flue gas humidification in a
5.3. Influencing factors on sulfur removal downstream wet precipitator [111]. A LIFAC process
in coal briquettes combustion on grates (limestone injection into the furnace and activation of
unreacted calcium) has been developed by the Tempella
Company, which gives a total SO2 reduction of 70%
Many factors such as coal size, molding pressure,
[112,113]. The largest full-scale demonstration unit of the
ignition pattern, particle size and composition of sorbents
LIFAC process has been operated at SaskPower’s 300 MW
have effects on the sulfur retention efficiency in coal
Poplar River Power Station in Canada since 1990. A
briquettes combustion. A large-sized coal briquette provides combined process comprising furnace limestone injection,
a longer residence time of the SO2 gas in the particles and in-duct humidification and bag-filter capture gives a SO2
more chance for SO2 capture by the limestone [104]. reduction of 80% in a pilot-scale PCFB [114].
A briquette prepared under lower molding pressure with It should be noticed that even for the same in-furnace
finer sorbents has a better desulfurization capability. desulfurization process, differences in SO 2 removal
Ignition at the bottom of briquette gives a higher sulfur efficiencies among pilot facilities probably occur due to
retention efficiency than ignition at the top, due to the larger variations in the following various parameters: temperature
reducing region in the coal bed where CaS is formed as a of the injection location, mixing of sorbent particles with
thermally stable sulfation product [105]. It is found that SO2 gas, residence time of sorbents in the furnace, cooling
calcium hydroxide and scallop shell both have better quench rate of the combustion gases and the sorbent
desulfurization capabilities than limestone, because calcium properties [45]. In general, the turbulent velocity,
hydroxide has lower calcination temperature and temperature field, particle and gas concentration
scallop shell has larger porosity after calcination [106]. distribution, and sulfation reactions all have certain effects
Also, adding some alkali or transitional metal compounds on sulfur removal in furnaces [115]. It is found that the
into limestone gives an increase in desulfurization efficiency potential core length for the particle-laden jet in a sorbent
during coal briquette combustion [107]. injection process is nearly twice as large as that for the
In summary, if only chemical compositions or physical single-phase flow. Recirculation of the particle-laden flow
properties of sorbents are improved, the ability to promote occurs downstream from the axial location where all
sulfur removal efficiency is very limited during coal concurrent flow is entrained into the diverging jet before
combustion on grates. The two-stage desulfurization process the jet hits the duct wall [116]. Owing to the great difficulties
in coal bed and combustion gas is competitive with regard to in investigating the details of sulfation course by
cost effectiveness. Although its market niche is likely to be experimental means under variable combustion conditions,
limited to smaller industrial boilers or existing boilers with it is probably more feasible to perform numerical
394 J. Cheng et al. / Progress in Energy and Combustion Science 29 (2003) 381–405

simulations to clarify the complex gas – solid reaction 6.4. Effects of porosity structure on sulfur removal
mechanisms in an in-furnace sorbent injection process. in the limestone injection process

6.2. Activation methods in preparation of reformed sorbents The particle size and pore size distribution both have
important effects on high-temperature and short-time
In order to promote reaction activities of sorbents for sulfation reactions. It is reported that pore diameters of
sulfur removal, it is effective to improve their physical 5– 30 nm are desirable for particles larger than 1 – 2 mm, as
properties by controlling the operational parameters in the shown in Fig. 11 [123]. For superfine limestones, the pore
preparation process. It is reported that introducing CO2 gas volume located in larger pores that are greater than 5 nm
into Ca(OH)2 suspension solution produces a reformed contributes to a high SO2 removal and CaO conversion,
CaCO3 with surface area of 10 – 70 m2/g, which has higher in addition to other parameters such as particle size and
surface area [75]. The plate-like pore geometry developed
sulfation capability than limestone [117]. When calcium
by some limestones and calcium hydroxides has been shown
lignosulfonate or ethanol – water solution is used in the CaO
to have several advantages over the cylindrical shape,
hydration process, the porous structure of calcium
producing a higher sorbent reactivity and delaying pore
hydroxide is improved and the particle size is decreased,
plugging. Very similar product layer diffusion coefficients
which leads to better SO2 capture [118]. Furnace sorbent
are obtained for calcium carbonate and for calcium
injection in a slurry form is found to increase sulfur removal
hydroxides, with activation energies ranging from 20 to
by lessening sorbent sintering due to evaporation of the
27 kcal mol21 [124]. A model based on fractal geometry
slurry droplets and by reducing sorbent particle size in the
suggests that the average pore radius decreases with a
slurrying process [119].
reduction of the fractal dimension, when the specific surface
Because there are some alkali and alkaline earth
area of calcined limestone increases. The optimum
compounds in coal ash, it is feasible to make use of them
utilization is achieved when limestone is calcined to a
to prepare low-cost sorbents for sulfur removal. The key
structure with fractal dimension between 2.5 and 2.7 [125].
problem is to activate the effective compositions in coal ash,
The sorbent utilization achievable for reaction times of
generally by a hydration process of Ca(OH)2 and coal ash
practical interest increases with surface area, because the
under elevated pressure. Hydration promotes the yield of
formation of a thin product layer over a large surface area
calcium aluminate silicate and results in an improved
leads to a high conversion of the solid [126]. Some
microstructure. The sorbent surface area has a linear
distributed pore models and random pore models have
dependence on the ratio of coal ash to Ca(OH)2, hydration
been developed to analyze the simultaneous calcinations,
time and other operational parameters [120]. It is reported
sintering and sulfation processes suffered by small
that the ratio of coal ash to Ca(OH)2 have significant effects
limestone particles injected into the post-flame zone of
on the surface area that varies in the range 2.5– 64.3 m2/g
PCFB to reduce SO2 emissions [124,127].
and on the calcium content that varies in the range
6 – 748 mg/l. It has little effect on the pore volume that
6.5. Fouling and slagging problems on hot surfaces
averages 1.1 cm3/g [121].
in the sorbent injection process

6.3. Effects of particle size on sulfur removal The sorbents injected into combustion gas react with SO2
in the limestone injection process as the combustion gas cools, eventually escaping from the
furnace and being captured by the downstream dust catcher.
It is recognized that smaller sorbent particles give higher This process significantly increases dust burden and may
SO2 reduction and CaO conversion. A sulfur removal well enhance fouling and slagging on hot surfaces, as well as
efficiency of 50% can be obtained by a furnace injection having important implications for particulate collection and
process with limestone particle size of 5 – 100 mm. ash handling equipments.
The grinding cost and destruction of pore volume, if sorbents The pyrite, alkali and alkaline earth sulfates and
are ground too fine, decide a minimum mean diameter of chlorides in coal ash promote the fouling and slagging on
approximately 5 mm [6]. A decrease in limestone mean hot surfaces, while in situ sulfation has some effects on
diameter from 10 to 1 mm promotes the SO2 capture from 40 deposit formation during coal combustion [128]. A sintering
to 50% at Ca/S ¼ 2 [42]. The sulfation reaction rate of process under limestone injection conditions results in
ultrafine CaO particles ðdp , 0:1 mmÞ is found to be superheater deposits, where CaO or partly sulfated CaO
5 £ 102 2 5 £ 103 times higher than that of conventional particles grow together by interactions with the flue gas.
CaO particles ðdp . 1 mmÞ used in dry injection processes The gas composition, local temperature and initial degree of
[122]. It is speculated that diffusion resistance inside a sulfation have influences on the sintering tendency of CaO
particle is eliminated with particle size of 1 – 2 mm, and particles, in which gas composition is an important
further reduction in particle size gives no additional benefit determinant. When air-cooled probes are inserted into the
[42,117]. superheater area of a 500 MW PCFB with time injection in
 J. Cheng et al. / Progress in Energy and Combustion Science 29 (2003) 381–405 395

Fig. 11. Model simulations of the impact of particle size and pore size distribution (10008C, 1000ppm SO2, 2s, Ca/S ¼ 1, 1CaO ¼ 0.5 in the
EFR) [123].

the upper furnace in order to collect samples of short-term combustion with desulfurization processes, it is essential to
deposits, it is found that severe deposition is always evaluate their granulometry, morphology, chemical
associated with high contents of either CaSO4 or CaCO3 composition, mineralogy and behavior to water contact.
in the deposit [74]. Their potential utilization is reported as road subbase,
landfill, embankment, brick material, cement components
6.6. Influence of sorbent injection processes and so on [132,133]. The dry desulfurization by-product
on dust catching from a LIMB process contains substantial portions of
available lime and may prove amenable as a solidifying
A high-temperature sorbent injection has some effects on agent with the fly ash [134]. The hydration reactions of FBC
particulate properties in the flue gas, such as electrical ash are dominated by sulfate chemistry that is the formation
resistivity, mass loading, size distribution, morphology and of gypsum and ettringite. The FBC ash treated via the
cohesiveness. The particulate electrical resistivity increases CERCHAR process and combined with pulverized fly ash
substantially and the electrostatic precipitator performance appears to make portlandite available for sulfo-pozzolanic
degrades accordingly when a sorbent injection process is reactions, which result in superior performance in
applied to a boiler burning medium- to high-sulfur coal. application as a cement substitute [135]. The fly ash derived
Using flue gas humidification or conditioning with SO3 may from a conventional PCFB with a lime injection process and
bring the resistivity back to an acceptable level. The fly ash from a circulating FBC with a limestone injection process
and sorbent mixtures derived from a sorbent injection presents some similar features: fine granulometry, presence
process contain rougher particles and tend to be more of anhydrite phase and sulfate content. However, PCFB ash
cohesive, compared to ordinary fly ash. Sorbent injection has many spherical particles and a much higher lime content
does tend to shift the particle size distribution towards finer due to the lower desulfurization efficiency, while most of
particles [129]. Combining a downstream ceramic filtration the trace elements in PCFB ash show an inverse concen-
or a flue gas dry scrubbing with a furnace injection process tration-particle size dependence, compared to FBC ash.
can improve the sulfur capture and dust collection The leachates obtained from both samples are rich in soluble
performance in a cost effective manner [130,131]. salts of CaSO4 and Ca(OH)2, but arsenic and selenium are
prevented from dissolving by a high lime content. In wetted
6.7. Reutilization of in-furnace desulfurization residues PCFB ash, the formation of ettringite crystals stabilizes
calcium and sulfate ions, while arsenate, selenate and
In order to identify the potential disposal and utilization chromate anions are trapped in the crystals. The FBC ash
options for the high-volume solid residues derived from coal does not really harden because the lime content is too low,
396 J. Cheng et al. / Progress in Energy and Combustion Science 29 (2003) 381–405

and the leached selenium concentration is reduced in wetted

FBC ash [136].
In summary, the sorbent injection process is competitive
in controlling SO2 emissions derived from PCFB, with a low
cost, a simple process and average efficiency. It is necessary,
however, to further clarify the step-by-step courses in
high-temperature sulfation reactions based on the chemical
thermodynamics, kinetics and thermal conditions. In order
to commercially popularize the in-furnace desulfurization
technologies, it is important to solve the fouling, slagging,
ash loading and residue utilization problems.

7. Sulfur removal under unconventional atmospheres

at high temperature

7.1. Desulfurization under reducing and oxidizing

atmospheres

The reactions between limestones and SO2 under

Fig. 13. Phase diagram for the system composed of CaO, CaSO4,
periodically changing oxidizing and reducing conditions in CaS, SO2, CO and CO2 in FBC.
FBC boilers have been extensively studied by many authors
[137 – 167]. It is found that the dense bed is under reducing
conditions (PO2 , 10211 bar) for 80 – 90% of the time, 7.1.1. Reducing and oxidizing atmospheres
which may be caused by a bypass of the fluidization air in in industrial grate furnaces
bubbles and jets through the dense bed. The variable To meet the demand of SO2 reduction during coal
parameters of alternating conditions include total reaction combustion, it is valuable to study the distribution of gas
time, cycle period, time fraction and composition of compositions and bed temperature in grate furnaces. For a
reducing atmosphere, etc. The sulfation reactions under fixed-bed grate furnace ignited at the bottom, the coal bed
alternating conditions follow a conversion circulation, as can be divided into four layers from bottom to top, the ash
shown in Fig. 12 [158]. The consumption of O2 gas and layer, reducing layer, oxidizing layer and fresh fuel layer.
reducing decomposition of CaSO4 have great effects on the That is to say, there exist changing oxidizing and reducing
sulfation efficiency. The CaS produced in a reducing atmospheres in the coal bed along the height direction.
atmosphere is further converted to CaSO4 or SO2 in an As shown in Fig. 14, with an increase in height, the O2
oxidizing atmosphere. The relative importance of the two concentration gradually decreases to nearly zero, while the
competitive reactions depends on local temperature and CO concentration gradually increases to some extent.
atmosphere, as shown in Fig. 13 [158]. The CO2 concentration and bed temperature first increase
and then decrease, reaching the peaks at the interface
between the oxidizing and reducing layers [168].
In the coal bed of a traveling grate furnace, there exist
various oxidizing and reducing conditions, not only in the
height direction but also in the grate-traveling direction.
The coal bed is ignited at the top before an estimated
diagonal line where volatile matter begins to release and
ignite, and it is ignited at the bottom after the dividing line.
There exist both oxidizing and reducing layers in the coal
bed for the two ignition patterns, but the thickness of the
reducing layer for the bottom-ignition pattern is larger than
that for the top-ignition pattern, which is favorable to more
effective sulfur retention [98]. As shown in Fig. 15,
the turning points of the profiles of gas composition just
above the coal bed correspond to the transitions of
Fig. 12. Solid phase transformations taking place when limestones the various combustion regions in the coal bed. In the
are exposed to alternating oxidizing and reducing conditions in grate-traveling direction, the O2 concentration firstly
FBC. decreases and then increases. On the other hand, the CO,
 J. Cheng et al. / Progress in Energy and Combustion Science 29 (2003) 381–405 397

effectively. The CaS phase produced in the reducing layer

and the CaSO4 phase produced in the oxidizing layer have
been identified in desulfurization residues derived from coal
briquette combustion [46,169]. How to make good use of
these oxidizing and reducing conditions to further promote
the sulfur retention efficiency is an interesting subject that
needs further research.

7.1.2. Reducing and oxidizing atmospheres

in pulverized coal fired boilers
SO2 emissions increase with the fuel equivalence ratio f in
fuel-lean combustion and decrease slightly when f . 1:2
[170]. The possibility of retaining sulfur in a solid form such as
CaS during pulverized coal combustion has been investigated
by studying the oxidation of 10 mm CaS crystals in a
laminar flow oxidation furnace under simulated coal
combustion conditions [151,171]. For the conditions
studied (1127 8C , T , 1477 8C; 0 , PO2 , 0.02 Mpa;
0 , t , 0.25 s), the oxidation results in the formation of
CaO and CaSO4. It is apparent that the intrinsic oxidation rate
of CaS to CaO (2 to 3 £ 1025 mol cm22 s21) is of the same
order of magnitude as the carbon oxidation rate for semi-
anthracites (3 to 5 £ 1026 mol cm22 s21). The CaS oxidation
can lead to: (1) a possible limiting retention level due to
Fig. 14. Distribution of gas compositions and coal bed temperature protection afforded by the formation of a CaO–CaSO4 eutectic
in the height direction. at T . 1365 8C; or (2) possible full sulfur loss for the fine CaS
H2 and SO2 concentrations firstly increase to their peaks and particles because of the high porosity of CaO product layer. The
then decrease [88,168]. experiments and thermodynamic predictions indicate that
The changing oxidizing and reducing conditions in the sulfur retentions of 90% can be obtained at particle
coal bed make it possible to capture SO2 on grates more temperatures above 1227 8C even with CaS fully exposed to
the flue gas, under fuel-rich combustion. Coal moisture has a
strong effect on the retention level due to the formation of
H2S. For fuel-lean combustion, retention can occur with
calcium dispersed within the burning coal due to a local
reducing atmosphere when carbon is present. Because the
oxidation rate of CaS is slower than that of most coal chars, high
reactive coals may be suitable for sulfur retention as CaS [172].
Based on equilibrium calculations for the coal/water/li-
mestone/air system (50 gas-phase and 6 solid-phase
chemical species), a staged sorbent injection process is

Fig. 15. Distribution of gas compositions in the grate-traveling

direction. Fig. 16. Schematic of a staged sorbent injection process in a PCFB.
398 J. Cheng et al. / Progress in Energy and Combustion Science 29 (2003) 381–405

proposed to control emissions derived from PCFB, as shown

in Fig. 16 [173]. Some sorbents are blended with feed coal
and injected by primary air into the furnace at high
temperature of 1500– 1600 8C, while other sorbents are
directly injected into the upper furnace at lower temperature
of 1100– 1200 8C. This process involves successive sulfur
retention as an intermediate product CaS in the high-
temperature reducing zone and as a final product CaSO4 in
the low-temperature oxidizing zone. This enhances the Fig. 17. Schematic of O2/CO2 coal combustion.
in-furnace desulfurization efficiency to 80 – 85%. In
practice, the staged sorbent injection process is
accompanied by the air-staged combustion pattern that is 850 8C. This far exceeds the maximum allowable
employed to reinforce the high-temperature reducing conversion level (about 55%) when the pores of calcinated
atmosphere and reduce NOx emissions. The optimal values limestone are completely plugged by the product CaSO4.
for air excess coefficient and molar ratio Ca/S for the first However, increasing the particle size from 53 – 62 to
desulfurization stage in zone I are, respectively, 0.7– 0.8 and 88– 105 mm decreases the conversion level by more than
1 – 1.5, which gives a sulfur removal efficiency of 40 – 50% 50%. For the 88 – 105 and 297– 350 mm particles, the effects
in this case. With an increasing amount of O2 and cooling of of particle size on the conversion curves are in quantitative
the flue gas, the conversion of CaS to CaSO4 increases and is agreement on a relative basis [8]. It is reported that
completed at an air excess coefficient of 1.2 in zone III. increasing temperature under high CO2 concentration favors
This air requirement and Ca/S molar ratio of 2 – 2.5 are reforming the microcosmic structure of calcinated sorbents
optimal for CaSO4-based desulfurization. [178,179].
It is promising to apply the staged sorbent injection Coal combustion with O2/CO2 is promising because of
process combined with air-staged combustion pattern to its high desulfurization efficiency, in addition to an
power station PCFBs. But it is necessary to further study the extremely low NOx emission and easy CO2 recovery.
sulfation mechanisms under varying reducing and oxidizing In this novel process, 80% of the flue gas is extracted before
conditions at high temperatures, especially the formation the dust catcher and is recycled into the furnace near the
and conversion of the intermediate product CaS and the final primary air combustor. This results in much higher
product CaSO4. concentration of CO2 and SO2 in the combustion gas, as
shown in Fig. 17 [180]. It is indicated that the
7.2. Desulfurization under O2/CO2 conditions desulfurization efficiency in O2/CO2 pulverized coal
by flue gas recirculation combustion, which reaches about 70 – 80%, is enhanced to
about four to six times over that of conventional pulverized
A high CO2 concentration is beneficial to SO2 capture by coal combustion, as shown in Figs. 18 and 19. It is mainly
a furnace sorbent injection process during coal combustion, attributed to the following factors: (1) the practical
compared to normal concentration at high temperatures and residence time of SO2 is extended and SO2 is enriched
usual sulfation times [174]. This can be explained by
minimizing sintering of CaO and plugging of reaction
product CaSO4 [175]. When the CO2 partial pressure is
higher than equilibrium, the calcination of limestone is
restrained, and limestone is subject to the direct sulfation
reaction: CaCO3 þ 1/2O2 þ SO2 ! CaSO4 þ CO2 [176].
The rate of direct sulfation does not decrease as much with
sulfation degree as it does CaO – SO2 sulfation, because
sintering is quite mitigated during direct sulfation of
limestone. The diffusivity in the product layer demonstrates
the high temperature dependence and hardly changes with
sulfation degree. This is associated with the fact that the
product CaSO4 layer is porous owing to CO2 formation
[177]. Because the particle size is found to have a very
strong influence on the rate of direct sulfation, which is
much stronger than that on the calcined sorbent reaction,
the conversion levels attained by larger particles are much
lower for the direct sulfation reaction. It is reported that the Fig. 18. Effect of temperature on system desulfurization efficiency
conversion level of 53 – 62 mm Greer limestone can reach under 1.2 oxygen-fuel stoichiometric ratio, 8 s one-pass residence
about 79% during direct sulfation for long exposure time at time, (Ca/S) ¼ 5 and 1.0 £ 1025 m limestone diameter.
 J. Cheng et al. / Progress in Energy and Combustion Science 29 (2003) 381–405 399

temperatures of 1200– 1600 8C, which have much lower

desulfurization efficiencies than those in fluidized bed
combustors. The SO2 reduction without sorbents during
coal combustion, thermal stabilities of sulfation products,
kinetics of sulfur retention reactions of sorbents, desulfuriza-
tion processes in IGF and PCFB, and sulfur removal under
unconventional atmospheres at high temperatures are
reviewed. It is proposed that some powdered minerals or
industrial wastes with effective metal components may be
used as sorbents for sulfur removal to promote cost
effectiveness. It is interesting to study the chemical
compositions, crystal structures, sulfation and kinetic
catalysis properties of the possible substitute sorbents.
Because the main reason for low desulfurization efficiencies
in IGF and PCFB is the thermal decomposition of CaSO4
Fig. 19. Variation of system desulfurization efficiency with
above 1200 8C, it is key to explore new sulfation products that
residence time of particles at 1400 K under 1.2 oxygen-fuel
stoichiometric ratio, (Ca/S) ¼ 5 and 1.0 £ 1025 m limestone
are more thermally stable. The kinetic catalysis of alkali and
diameter. transitional metal compounds on sulfation reactions is also
important under combustion conditions, considering the
inside the furnace owing to the flue gas recirculation; short residence time and decreasing surface area of
(2) CaSO4 decomposition is inhibited because of the high calcinated limestones at high temperature. Although SrSO4,
SO2 concentration. These contributions are quantitatively BaSO4, 3CaO·3Al2O3·CaSO4 and Ca5(SiO4)2SO4 are ther-
clarified as follows: below 1177 8C, the former contributes mally stable at temperatures over 1300 8C, it is difficult to
above two-thirds, whereas above 1227 8C, the latter take effective measures to promote the yields of such
contributes above two-thirds to the overall increase in products during coal combustion in furnaces, due to the
low content of such reactants. In the normal Ca – S– O
desulfurization efficiency [181]; (3) the direct sulfation of
reaction system, a-CaSO4 is thermally stable under oxidizing
limestone under high CO2 concentration; (4) the unreacted
conditions below 1495 8C and so is CaS under reducing
calcium in the flue gas is reutilized by recirculation.
conditions below 2400 8C. It is promising to utilize the
The system desulfurization efficiency in O2/CO2 pulverized
temperature and burning gas distribution to produce CaS and
coal combustion maintains a high value over a wide range of
a-CaSO4 phases as sulfation products in furnaces.
temperatures and particle residence times. The flue gas
Simply blending sorbents with feed coal to capture SO2
recirculation decreases the flame temperature, which also
gas during combustion on grates gives desulfurization
results in a lower yield of thermal NOx. After many cycles of
efficiency lower than 40%, which also declines with an
recirculation, the CO2 concentration in the flue gas reaches
increase in furnace size and flame temperature. Burning coal
about 80%, which can be extracted and purified by a special
briquettes with sorbents on grates or injecting sorbents into
installation before exhaust [175].
the furnace can give moderate desulfurization efficiency that
Although there still exist many unknowns about the
are generally lower than 60%. It is proposed that the
desulfurization mechanism in O2/CO2 pulverized coal
two-stage desulfurization process, viz. SO2 is captured by
combustion systems, it is very promising and inspiring to
sorbents both in the coal bed and in the combustion gas,
further develop this novel and artful process that gives a
is promising for IGF, which gives an in-furnace
high desulfurization efficiency of 70 – 80%. Because
desulfurization efficiency over 70% and a total SO2
current research on this new process is limited to small
reduction of higher than 85% after the flue gas humidifi-
lab-scale furnaces, it is necessary to carry out further
cation in a water-film dust catcher. For PCFB, injecting
pilot-scale and full-scale experiments to evaluate its
limestones into the furnace through a low NOx burner or by
feasibility for power station PCFBs from the technical
a special nozzle only gives sulfur removal efficiency of
and economic view.
25– 50%. Installing a large humidification tower before the
dust catcher, a LIFAC process can give an overall
desulfurization efficiency about 70% after the hydrated
8. Conclusions activation of unreacted calcium. It is proposed that the
staged desulfurization process combined with an air-staged
In-furnace desulfurization is a competitive technology for combustion pattern, in which sorbents are injected into the
controlling the SO2 pollutants derived from coal combustion, primary air field and the upper furnace to capture SO2 under
due to the low capital and operating costs contrasted to flue reducing and oxidizing atmospheres, is promising for PCFB,
gas desulfurization techniques. This paper focuses on sulfur and so is the desulfurization process by flue gas recirculation
removal processes in IGF and PCFB with high flame under O2/CO2 conditions. It is valuable to study further
400 J. Cheng et al. / Progress in Energy and Combustion Science 29 (2003) 381–405

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