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

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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 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2. SO2 reduction without sorbents during coal combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1. Blending coals to control the sulfur content. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2. Self-desulfurization of coal ash during combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3. Thermal stabilities of sulfation products of sorbents at high temperature . . . . . . . . . . . . . . . . . . . . . . . 3.1. Alkaline earth sulfates as the stable desulfurization products . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2. Calcium aluminate sulfate as the stable desulfurization product . . . . . . . . . . . . . . . . . . . . . . . . . 3.3. Calcium silicate sulfate or Fe –Si – Ca melt enwraping CaSO4 as the stable products . . . . . . . . . . 4. Kinetics of sulfur retention reactions of limestones at high temperature. . . . . . . . . . . . . . . . . . . . . . . . 4.1. Calcinations and sintering of limestones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2. Sulfation kinetics of limestones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.3. Kinetic catalysis of alkali compounds on sulfation reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . .
* Corresponding author. Tel.: þ 86-571-879-52889; fax: þ 86-571-879-51616. E-mail address: juncheng@cmee.zju.edu.cn (J. Cheng). 0360-1285/03/$ - see front matter q 2003 Elsevier Ltd. All rights reserved. doi:10.1016/S0360-1285(03)00030-3

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

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1. Introduction Sulfur pollutants derived from coal combustion are harmful to the environment. China is foremost in the 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 industrial grate furnaces (IGF). Among the various kinds of desulfurization technologies, sulfur removal in furnaces is competitive for controlling the SO2 pollutants derived from coal combustion, due to the low capital and operating costs. But it has met difficulties in becoming popular commercially, because of the initially low desulfurization efficiency. The main obstacle is that the flame temperature in PCFB is about 1300– 1600 8C and that in IGF is about 1200– 1400 8C, which are much higher than the thermal stability temperature of the sulfation product CaSO4. This paper focuses on the latest development of desulfurization technologies in IGF and PCFB that solve this problem. 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 temperatures are reviewed. The pre-combustion desulfurization processes such as coal washing, liquefaction and gasification are beyond the present scope of discussion, as well as the post-combustion desulfurization processes such as scrubbing flue gas with various solutions. Readers interested in the dry sorbent injection into the back-end fields such as economizers or air-heaters with temperatures of about 200– 500 8C are referred elsewhere [2 –6].

For sulfation phenomena in fluidized bed combustion systems (FBC) with temperatures of about 800– 900 8C, a recent comprehensive review has been given by Anthony [7] with further detailed information elsewhere [8 – 19].

2. SO2 reduction without sorbents during coal combustion 2.1. Blending coals to control the sulfur content A variety of low- and high-sulfur coals from various sources can be blended in different proportions to meet normal and optimal limits for SO2 emissions [20]. As sulfur contents are directly proportional in blending, the blend ratio of component coals can be determined based on sulfur content to meet emission levels [21,22]. A simple goal programming model is developed with an objective to provide a decision support system. It determines appropriate quantities of coal from different stockpiles for a consistent feeding of blended coal while meeting environmental and boiler performance requirements [23]. Although a sequence of linear programs can give a blend ratio to achieve the predicted sulfur content, it can not ensure a good combustion or slagging performance of the blended coal [24]. It is shown by experiment that some characteristic parameters of a blended coal such as ignition temperature and burnout efficiency cannot be predicted from component coals by arithmetic averaging [25]. An overall grey clustering model that takes into account the main related parameters such as ash characteristics, mineral

In order to obtain an optimum blend ratio. Due to the high flame temperature of about 1300–1600 8C and short residence time of about 1 – 2 s. the mixed discrete-variable optimization design algorithm is employed to solve the coal-blending project. it is difficult to realize the optimization in each parameter of a blended coal. but less for the new samples. The mineral transformation during coal blends combustion is affected by both the mineral species interaction and the combustion behavior. this statement is questionable. a reasonable ratio index of price to quality also can be introduced. Compared to the traditional techniques such as the ternary equilibrium phase diagrams and regression relationships. K2SO4. The characteristic parameters such as heating value. The desulfurization property of coal ash during combustion is mainly affected by the boiler shape. the modeling process in the BP networks is much more convenient and direct. a coal blending expert system is developed to realize the multi-target optimization.2. A case-by-case evaluation must be made in order to determine whether limitations imposed by blending coals are acceptable to the user’s situations. It is obtained by calculation that the content of glassy noncrystal phase is about 70%. it is found by X-ray powder diffraction (XRD) analysis that the CaSO4 phase is the main sulfation product retained in fly ash for a PCFB. However. Na2O in coal ash. the model can give rather precise prediction for the trained coal samples. It is reported that the self-desulfurization efficiency of Shenmu coal sharply . Therefore. A back-propagation (BP) neural network is introduced into this coal blending optimization to accurately predict some non-linear coal properties such as ash fusion temperature. Also. such as MgSO4. flame temperature. In my opinion. the contribution of calcium is reduced markedly. due to the restrictions of component coals. The higher the steam load or flame temperature. Some combinations of component coal’s mineral produce low-melting eutectic minerals at high temperature and this is the main reason causing the non-arithmetic averaging of ash fusion temperature of blends [27. for there is no necessity to specify a mathematical relationship between the input and output variables. to act as the sulfation products during coal combustion at high temperature. The results suggest that when one coal is blended with another coal with widely different reactivity or slagging potential. But in a PCFB. ignition temperature and burnout efficiency are taken into account in the system. coal ash generally gives a desulfurization efficiency of lower than 25% in a PCFB [37]. whereas most of them are sulfides under reducing conditions [36]. a long residence time of particles and a good gas– solid contact condition.7 and 2. On the other hand. the lower desulfurization efficiency is. initial molar ratio of Ca/S and reaction activity of alkaline components. With a suitable furnace temperature of about 800–900 8C. a FBC gives a higher selfdesulfurization efficiency than a IGF or PCFB even for the same coal. Furthermore. ash content and sulfur content [35]. As a complex regression method in nature. power coal blending process has been considered extensively. It is necessary for boiler operators to evaluate the conversion percentage of feed sulfur into gaseous pollutants and select a proper desulfurization process to meet the Clean Air Act. while the contributions of other elements are limited. The alkaline sulfates are dominant at lower temperatures under oxidizing conditions. volatile matter. residence time in the furnace. volatile matter. the content of melted non-crystal phase is only about 26% and no CaSO4 phase is detected in the bottom ash [38]. Application of this novel coal blending technology indicates that it is much more useful and reasonable to guide blend production than the traditional methods [32 –34]. The XRD pattern of fly ash derived from Shenmu coal combustion in a 1000 t/h PCFB is shown in Fig. respectively. the slagging grade of the coal blends changes significantly [26]. 2. Na2SO4 which are less thermally stable than CaSO4. Based on a non-linear programming model. and the content of remained active CaCO3 and CaO phases are. ash fusion temperature. Moreover. the content of self-desulfurization product CaSO4 phase is 3. / Progress in Energy and Combustion Science 29 (2003) 381–405 383 transformation. calcium should play a dominant role in sulfur retention of coal ash not only in the laboratory but also in a PCFB. less than 10% is retained in the fly ash and less than 1% is held in the bottom ash.2%. and combustion parameters is proposed to predict the slagging propensity of the blends. As a viable cost-effective alternative to comply with environmental considerations. and generally no sulfates of other elements are detected. A Coal Quality Expert system has been developed by ABB/CE company for controlling coal cleaning or blending to provide clean coal products [31]. which is based on BP neural network models for some complex quality parameters of blends. the trained BP model can always achieve much better prediction results than traditional methods [29. while the roles of other alkaline elements are enhanced [37]. Fe2O3. due to the contribution of alkaline components such as CaO.J. sulfur content. about 60% of feed calcium is retained in the fly ash and less than 10% is found in the bottom ash. Self-desulfurization of coal ash during combustion Most organic sulfur and pyrite in coal are oxidized and converted to SO2 gas during combustion in furnaces. ash content. Al2O3. It is pointed out that calcium plays a dominant role in sulfur retention of laboratory-prepared ash. A small part of the sulfur may be retained as solid compounds. MgO. Cheng et al. ignoring the changes in combustion and slagging performances. It is difficult for the sulfates of other minor elements.30]. Al2(SO4)3.4%. K2O. Fe2(SO4)3. But it is subject to error and insufficient to consider only the sulfur pollutant emissions in coal blending. simultaneously considering the influences of heating value. 1. It is indicated that about 70% of feed sulfur is turned into SO2 gas.28]. 4. In accordance with the actual blend production process.

there Fig. Cheng et al. 2. According to XRD analysis. because of their complete decomposition. 3 [37. as shown in Fig. / Progress in Energy and Combustion Science 29 (2003) 381–405 Fig. Neither active CaCO3 and CaO phases nor sulfation product CaSO4 phase remain in Shenmu coal ash prepared at 1200 8C. the content of sulfation product CaSO4 phase reaches 18% in Shenmu coal ash prepared at 800 8C. XRD pattern of fly ash derived from coal combustion in a 1000 t/h PCFB. A general trend can be found that the sulfur retention efficiency of coal ash is promoted by an increase in molar ratio of Ca/S. .384 J. Most of the free calcium ions Ca2þ in raw coal ash are converted into a part of the melted glassy matter and entirely lose their activity [38]. However. 2.40]. 1. decreases from 63 to 6% in a tubular furnace. XRD pattern of Shenmu coal ash prepared at 1200 8C.39. while the total content of remaining CaCO3 and CaO phases is 22%. with an increase in furnace temperature from 800 to 1200 8C. as shown in Fig.

calcium aluminosulfate (3CaO·3Al2O3·CaSO4) and calcium silicate sulfate (Ca5(SiO4)2SO4) may act as thermally stable sulfation products at high temperatures as .J. a self-desulfurization efficiency of 28. barium sulfate (BaSO4). the ratio of Ca/S in Shenmu coal (sulfur content ¼ 0. is some scattering in regression of sulfur retention of lab-prepared coal ash against Ca/S molar ratio.1 and 0. and so is the calcium that has the ability for sulfur retention. 1. that are much lower than in FBC of 850– 900 8C.4% is obtained in a lab-scale PCFB [41]. Correlation of sulfur retention by coal ash with initial Ca/S molar ratio. The key problem that controls the sulfur removal efficiency is the thermal instability of the conventional sulfation product CaSO4 above 1200 8C. Cheng et al.6%).8% at 1100 8C. how to form thermally stable sulfation products is an important issue. For Shikantai coal with a high molar ratio of 4. strontium sulfate (SrSO4). It is valuable to further investigate the thermal behaviors of minor elements in coal ash and their affinities for sulfur during coal combustion.5. fly ash and bottom ash.1%) and Changguang coal (sulfur content ¼ 4. The self-desulfurization efficiency of Shenmu coal reaches 27 –33% in a 1000 t/h PCFB [38]. The calcium-based sorbents can only give low sulfur removal efficiencies during coal combustion in IGF with the flame temperature of 1200– 1400 8C or in PCFB of 1300– 1600 8C. mainly due to high combustion temperature and short residence time of particles. In order to develop highly effective sorbents suitable for sulfur removal at high temperatures. resulting 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 to sulfur retention. To explain this non-balance needs further research. which is of interest to boiler operators.3. which is much higher than that of Huangling coal (13. For example.7%) [38]. especially the furnace temperature. In a full-scale experiment. In a lab-scale tubular furnace. Thermal stabilities of sulfation products of sorbents at high temperature The desulfurization capabilities of limestones are strongly affected by thermal conditions. 3. From the point of view of chemical thermodynamics.3%) is. Shenmu coal achieves a sulfur self-retention efficiency of 23. 1.3%) and Changguang coal (13.0. The transformations of alkaline components in a PCFB are different from those in lab ashing process. / Progress in Energy and Combustion Science 29 (2003) 381–405 385 Fig. respectively. 3. it is difficult to obtain a mass balance between the feed sulfur in coal and the discharge sulfur in flue gas. Huangling coal (sulfur content ¼ 1.

alumina and CaSO4 at . With some impurities such as NaCl. As shown in Fig. There is still much to do to reform the composition and preparation of barium-based sorbents for more effective sulfur removal. It should be noted that CaSO4 has three allotropes that have different structures and chemical properties. The metastable and soluble g-CaSO4 is derived from the dehydration of CaSO4·2H2O at 130– 200 8C. CaS that is thermally stable at high temperature up to 2400 8C in reducing atmospheres [45] can also act as the sulfur retention product. It is shown by experiment that the decomposition percentage of CaSO4 increases with the increasing furnace temperature. Cheng et al.6% when CaCO3 is added into the coal with a molar ratio of Ca/S at 2. or from the reaction of CaSO4 with carbon at coal particle surfaces. It is shown by experiments that SrCO3 can promote the sulfur removal efficiency of limestone [47]. they have similar chemical and physical properties. It is well known that CaCO3 that rapidly decomposes at about 800 8C is often used as sorbent to capture SO2 to produce CaSO4. When BaCO3 content decreases and CaCO3 content increases. When CaO and some additives are added into coal briquette at Ca/S ¼ 2. the initial decomposition temperature of CaSO4 decreases.4 times that of Ca. with a constant sum of molar ratios of Ba/S and Ca/S at 2.8% in raw coal ash [46]. It scarcely decomposes below 1050 8C and only gives a decomposition percentage of 13 wt% at 1150 8C. SiO2 or steam. 40 – 60. Because BaCO3 rapidly decomposes at about 1300 8C and BaSO4 is more thermally stable than SrSO4. while the decomposition rate increases. This is higher than the sulfur content of 1. it is possible to make use of the temperature and atmosphere distribution to produce CaS or a-CaSO4 as sulfation products. The thermal stabilities of alkaline earth carbonates and sulfates gradually increase from magnesium to barium. 3. However. Calcium aluminate sulfate as the stable desulfurization product In terms of powder diffraction files published by JCPDS [49. Because the atomic weight of Sr is 2. SrSO4 that is thermally stable to temperatures up to 1580 8C will act as the sulfation product. Consequently. It is higher than the low sulfur removal efficiency of 10. It is the main constituent in sulfo-aluminous clinker. which indicates that 1200 8C is the turning point of the decomposition of CaSO4 [38].386 J. How to take effective measures to enhance the yield of the thermally stable SrSO4 during coal combustion needs further research. CaS can be produced from the reaction of CaO with H2S gas in a reducing atmosphere. it is more practical to blend expensive barium compounds with limestones for sulfur removal.50]. Alkaline earth sulfates as the stable desulfurization products Magnesium. strontium compounds are much heavier and more expensive than the corresponding calcium compounds with the same molar ratio to sulfur.2 times that of Ca. besides CaSO4.2.7% in a desulfurization residue obtained at 1300 8C.1. calcium aluminate sulfate (3CaO·3Al2O3·CaSO4) is a ternary compound. which is 3. it is found by XRD and X-ray fluorescence analysis (XRFA) that the CaS phase is the main sulfation product and retains a sulfur content of 4. The reason why dolomite gives a higher desulfurization efficiency than limestone is that inert MgO crystals disperse the smaller CaO crystals. a sulfation product SrSO4 phase is detected in the combustion residue [48]. respectively. / Progress in Energy and Combustion Science 29 (2003) 381–405 well as CaSO4 and CaS. which can promote SO2 reduction from the flue gas in IGF or PCFB. the sulfur removal efficiency of sorbents gradually declines. it is not suitable to act as the sulfation product under combustion conditions in IGF or PCFB. adding BaCO3 with a molar ratio of Ba/ S at 2 gives a high sulfur removal efficiency of 44. The traditional limestone. When 0. Ca(OH)2. it is possible to use BaCO3 as a sorbent for sulfur removal to obtain the sulfation product BaSO4 at high temperatures. Because there exist local reducing regions under otherwise total oxidizing conditions in industrial furnaces. The a-CaSO4 obtained at high temperature is thermally stable from 1210 8C up to its melting point of 1495 8C [44]. It is synthesized by heating a mixture of lime. 5 [38]. But the decomposition percentage dramatically increases to 57 wt% at 1200 8C and 96 wt% at 1300 8C. 3. It is shown by experiments that barium ion Ba2þ has better desulfurization capability than calcium ion Ca2þ at high temperatures of 1200–1300 8C. It is still better to prepare new sorbents composed of large amount of limestone and a little of SrCO3. which leads to a higher porosity in calcined dolomite during the sulfation procedure [43].5% during coal combustion at 1250 8C in a tubular furnace. 40 – 60 and 50 – 65% in a furnace injection process [42]. dolomite and dolomitic hydrate.2 wt% SrCO3 and 8 wt% CaO are added into the coal. If SrCO3 or Sr(OH)2 is used as sorbents to capture SO2 gas during coal combustion. including the sulfur retention capability. It is known that the decomposition of CaSO4 is accelerated in a reducing atmosphere or at carbon surfaces. calcium. as shown in Fig. strontium and barium all belong to the alkaline earth metal group. although these also have some defects for sulfur removal during coal combustion which needs further examination. give desulfurization efficiencies of 30 –45. In a normal Ca –S– O reaction system. But due to the higher atomic weight of Ba. b-CaSO4 is produced from g-CaSO4 at 300 8C. which is used as an expansive agent in manufacturing expansive cement. 4. which kind of CaSO4 formed during coal combustion and how to promote the yield of a-CaSO4 are interesting subjects and need further research. while carbonate radicle 2 2 CO2 3 excels hydroxide radicle OH . Because MgSO4 completely decomposes at about 750 8C when carbon exists.

Al2O3 and CaSO4 with the molar ratio of 3:3:1 gives a high sulfur retention efficiency at about 1300 8C. The crystal phase 3CaO·3Al2O3·CaSO4 is detected in the desulfurization residue derived from coal briquette combustion. the possibility for the ternary compound to act as the sulfation product during coal combustion has been examined by various authors. Desulfurization with BaCO3 and CaCO3 during coal combustion. 1350 8C. / Progress in Energy and Combustion Science 29 (2003) 381–405 387 Fig. As calcium aluminate sulfate has better thermal stability than CaSO4. 5. the more 3CaO·3Al2O3·CaSO4 is formed and less SO2 pollutant is emitted [51]. an additive Fig. 4.J. . the finer reactant particles and longer reaction time. Although a mixture composed of pure CaO. To a certain extent. Desulfurization with barium compounds during coal combustion. as shown in Fig. 6. Cheng et al.

conditions. Compared to 2Ca2SiO4·CaSO4. Most authors have paid attention to the Fe – Si– Ca melt that physically enwraps the sulfation product CaSO4 so preventing its thermal decomposition. how to enhance the yield of 3CaO·3Al2O3·CaSO4 during coal combustion is a key problem. that still has many difficulties to overcome in practice. The former is mainly formed through a physical . calcium silicate sulfate Ca5(SiO4)2SO4 is more thermally stable and can act as a sulfation product during coal combustion at high temperatures. composed of CaO and Al2O3 gives only a low SO2 reduction from the flue gas during coal combustion [52]. are far from clear. 6. It forms in the flame area between the refractory lining (30% Al2O3 brick) and an outer layer of larnite in a lime kiln. It is found that simultaneously adding Fe2O3 and SiO2 into CaO can promote the sulfur retention efficiency from 46 to 65% during coal combustion at 1200 8C. XRD pattern of desulfurization residue derived from coal combustion.3. 2Al2O3·3SiO2 and a-Fe2O3 are found by XRD analysis in the desulfurization residue derived from coal combustion. This is mainly because of the other ensuing mechanisms that inhibit the formation of calcium aluminate sulfate. It is pointed out that Ca5(SiO4)2SO4 is synthesized from siliceous lime sand. 3. the Fe – Si– Ca melt enwraping CaSO4 or calcium silicate sulfate Ca5(SiO4)2SO4? It is still unknown. the formation mechanisms of Ca 5 (SiO 4 ) 2 SO 4 during coal combustion. 2Ca2SiO4·CaSO4 is prepared from calcium carbonate. the contribution of Ca5(SiO4)2SO4 to retain sulfur during coal combustion at high temperatures is uncertain. Unfortunately. Cheng et al. with a flame temperature of 1500– 1600 8C and a kiln-wall coating temperature of about 1100 8C [53]. extents and rates. It is shown by scanning electron microscope (SEM) and energy dispersive X-ray analysis (EDAX) that silicates with Si and Fe contents closely enwrap CaSO4 and prevent it from decomposing at high temperatures [56. This results from the formation of a new heat-resisting crystal phase CaFe 3 (SiO 4 ) 2 OH which enwraps the sulfation product CaSO 4 [55]. Calcium silicate sulfate Ca5(SiO4)2SO4 (from a very reliable JCPDS file: 26-1071) [44] and calcium silicosulfate 2Ca2SiO4·CaSO4 (from an uncertain JCPDS file: 18-307) [49] are interesting allotropes. with SO3 which is produced in the air-blast injection of fuel-oil with 3. Calcium silicate sulfate or Fe – Si– Ca melt enwraping CaSO4 as the stable products The high-temperature phase equilibrium in CaO– SiO2 – SO3 system is important in the chemistry of traditional cements. the reaction schemes. but is enwrapped by silicates melt. by ignition at 1150 8C for 150 h in a platinum –rhodium resistance furnace [54].388 J. Therefore.57]. Some individual phases such as CaSO4. CaSO4 does not form a solid solution with silicates at high temperatures. However. Which is the main sulfation product of silicates. which contains 83 wt% CaCO3 and 13 wt% SiO2.8% sulfur content. but no new sulfation compound containing silicon and ferrum is detected. Because of its crystal structure. crushed quartz and AnalaR CaSO4·2H2O which are finely ground to pass a 300-mesh sieve. / Progress in Energy and Combustion Science 29 (2003) 381–405 Fig.

But when the furnace temperature is lower than 1100 8C. Because the silicon compounds as inert mineral ingredients are harmful to coal combustion and promote the sulfur removal in a limited range. with increasing duration at the temperatures of 900– 1100 8C. Calcining different limestones under the same conditions yields different surface areas and porosities [67. The decomposition of limestone with the particle diameter of about 14 mm is mainly controlled by chemical reaction at 1000 8C. It is found that a kind of clay mineral can promote the desulfurization efficiency of CaCO3 from 16 to 31% during coal combustion at 1200 8C. Calcinations and sintering of limestones The porosity structures of calcined limestones are important for the high-temperature and short-time sulfation reactions in furnaces. and the decomposition of calcium hydroxide produces larger CaO surface area than calcination of limestone [65. Whether the Fe – Si – Ca sorbents are beneficial or harmful during coal combustion depend upon factors such as heating rate. In the calcination procedure of limestones with particle diameters of 9 –16 mm. adding silicon compounds into the fired coal sometimes may be harmful to sulfur removal under certain conditions. But the rate increases slowly below the critical Tamman temperature which is 0.1 – 0. residence time and reaction atmosphere.1% promotes the sulfur removal efficiency from 41. which leads to compact crystals with much lower reaction activities [70]. it should be noted that SiO2 cannot only form silicates that enwrap the sulfation product CaSO4. which is higher than that of 27 m2/g at 900 8C [62].6%. The fragmentation behavior is a function of sorbent type. especially when the temperature is above 1000 8C. In general.J. with the sorbent type being the dominant parameter. The calcined limestone obtains a maximum surface area of 47 m2/g at 1100 8C. it is not wise to add extra silicon compounds into the fired coal.68]. On the other hand. It is found that SO2 . Prolonged residence time also gives an increase in sintering rate.2 to 53. the Tamman temperature is about 1000 – 1250 8C. The surface area of calcined limestone depends on the calcination rate and sintering rate [69]. Hence. thus it is important to study the calcinations and sintering performance of limestones. It is useful to study how to activate these silicon ingredients to form thermally stable sulfation products for effective sulfur removal in furnaces.3 mm is enhanced by an increase in temperature and duration [72]. When Na2SiO3·9H2O is added into CaCO3 with a weight ratio of 0. and increases rapidly above it. while the latter is mainly formed through a chemical combination process. It is assumed by a reformed partly sintered globe model that calcination follows one class of reaction dynamics in a furnace sorbent injection (FSI) process [63]. the sulfur removal efficiency is promoted from 16 to 33% at 1200 8C. but other clay minerals such as bentonite and zeolite have little promotion effects for sulfur removal [60].5 times the melting temperature of solid.1. in which temperature is the most important factor. Kinetics of sulfur retention reactions of limestones at high temperature 4. The calcination mechanisms of limestones vary with particle diameters and furnace temperatures. There are large amount of silicon ingredients in coal ash. which can take part in the desulfurization reactions during coal combustion. The above discussions are based on the viewpoint that silicon compounds are beneficial to SO2 reduction from the flue gas. A number of efforts have been made to try to produce calcinated limestones with large surface areas. Even for the same limestone. For CaO crystal whose melting temperature is 2500 8C. It is reported that the sintering extent of CaO particles with diameters of 0. while decreases the efficiency at a constant furnace temperature of 1080 8C [58].66].8% at a constant heating rate from room temperature to 1080 8C. particle size and particle temperatures in the range of 600–1600 8C. Cheng et al. sintering rate accelerates with an increase in temperature. it is a challenge to clarify the reaction mechanisms. The sintering of calcined limestone results in a decrease in surface area and porosity. The atmosphere and impurities also have important effects on sintering properties of limestones. the surface area varies with the calcining conditions such as furnace temperature. It is reported that simultaneously adding Fe2O3 and SiO2 into CaCO3 with the same weight ratio of 0.4 – 0. the rate-controlling step is chemical reaction that follows the single-step nucleating mechanism [61]. It is found that dolostone is more susceptible to breakage than limestone [64]. The sintering characteristics of limestones are strongly affected by furnace temperature. It is reported that the surface area of limestone firstly increases due to calcination and then decreases due to sintering. while the decomposition of limestone with the particle diameter of about 91 mm at 1100 8C and that with the particle diameter of about 152 mm at 1200 8C is mainly controlled by CO2 gas diffusion [62]. but also form a CaO – SiO2 phase that has a low capacity for sulfur retention. The formation conditions of calcium silicate sulfate and Fe – Si – Ca melt enwraping CaSO4 are also not clear and affected by the variable combustion conditions. the sulfur removal efficiency is decreased [59]. 4. It is shown by experiment that the surface area of calcined limestone decreases sharply due to the increased sintering above 1100 8C [71]. furnace temperature and reaction activity of the silicates. / Progress in Energy and Combustion Science 29 (2003) 381–405 389 flow and enwrapping process. Because the high-temperature behavior of silicates during coal combustion is complicated and the identification of complex desulfurization phases needs advanced analysis techniques. duration and particle diameter.

When the furnace temperature is higher than 1200 8C. the second sulfur emission peak is dramatically . meeting SO2 and O2 at the outer surface of the CaSO4 product layer where reaction occurs. simply blending alkali compounds into the fired coal probably gives little promotion for sulfur removal at high temperatures in IGF and PCFB. In general. The ‘continuous’ product layer formed in the later stage is a monolayer of individual crystals with pore size of 2 – 3 nm along the boundaries. the activation energy required for SO2 formation is reduced.84]. a sufficient concentration of sodium impregnated in CaO produces a thin surface eutectic layer made up of NaCl/CaO that is highly active.75]. such as furnace temperature. It is reported that Changshan limestone has a better sulfur removal capability than Jiawang limestone or Tongshan limestone under the same conditions.2. Accepting the assumption that chemical reactions take place at the interface of the reactant and product layer. Sulfation kinetics of limestones The mechanisms of high-temperature and short-time sulfation reactions in a limestone injection process can be well characterized by a two-stage process with a very fast initial surface reaction and followed by a product layer diffusion controlled step for CaO – SO2 reaction. Due to the catalysis of FeCl3. A combination of the two mechanisms is also possible. that is chemical reactions may occur at both locations. Therefore. which increases the number of CaO sites that are readily available. residence time. In my opinion. whilst the conversion percentage of raw CaO is 20 wt% at 850 8C. due to the smaller particle diameter and larger surface area resulted from calcination and impurities [79]. due to the subsequent absorption effect of FeCl3. The reaction of CaO with sodium induces particle fragmentation and large cracks. the presence of CO2. Meanwhile. This results in that the two peak temperatures of sulfur emission are both reduced and their interval is enlarged. Chemical reaction is a rate-limiting step only in the early stage when a continuous product layer has not been formed. while the dynamic rate is secondary. Kinetic catalysis of transitional metal compounds on sulfation reactions Transitional metal compounds such as FeCl3 and Cr2O3 can also accelerate CaO sulfation reactions during coal combustion. Maximum conversion percentage is obtained when the NaCl content is about 2 wt% [80 – 82]. 4. With CO gas in the flue gas. In a limestone injection process. Cheng et al. It is found that the product ‘layer’ formed in the early stage of the reaction is not a true layer. In addition. The presence of the liquid phase increases the diffusion of SO2 in the product layer to inner unreacted CaO that is inaccessible in the solid phase. an unreacted nucleus usually remains in the partly sulfated CaO particle under furnace injection conditions.390 J.4.3. it is important to understand how and where the solid and gaseous reactants interact. the first sulfur emission peak derived from coal combustion with FeCl3 is higher than that without sorbent. When O2 and SO2 gases exist in the flue gas. This reaction mode has been assumed whenever the untreated core model or the grain model is applied. meeting CaO at the interface between CaO and CaSO4 where sulfation takes place. This is attributed to plugging of intraparticle pores and enveloping of particles by the product CaSO4. O2 or CO compositions in the flue gas produces various degrees of sintering of CaO particles. 4. SO2 partial pressure and molar ratio Ca/S. The reaction then declines markedly. One opinion is that SO2 and O2 penetrate inwards through the product layer by gaseous or solid state diffusion. the sodium compounds readily vaporize under combustion temperatures. sintering of the dust is reduced with a higher initial content of the sulfation product CaSO4. the limestones from different sources have different calcination and sulfation performances. 4. but a residence time of 2 s is still necessary to obtain a reasonable SO2 reduction [43. SO2. Also. Another opinion is that the solid reactant migrates outwards through the product layer by ionic diffusion. Kinetic catalysis of alkali compounds on sulfation reactions It is known that adding alkali compounds such as NaCl into limestones can promote the sulfur removal efficiency during coal combustion. the thermal stability of the sulfation products becomes the controlling factor. Evidence to support the latter mechanism is from sulfation reactions at 1300 8C. / Progress in Energy and Combustion Science 29 (2003) 381–405 and CO2 gases strengthen the sintering effects. and therefore promotes the overall conversion [83. where the dynamic rate is the determining factor for sulfur removal. The product layer is more porous when developed from larger stable nuclei formed during the initial reaction at higher temperature and lower SO2 concentration [76 – 78]. which contains NaCl up to 3 wt%. It is reported that the conversion percentage of CaO.3 s. Extensive sintering occurs with CO2 compositions. FeCl3 acts as both a catalyst and an absorbent in conversion of sulfur in coal to SO2. a crystallization and fracture model is developed based on free energy-work analysis. as do impurities such as Fe2O3. The sulfation reactions are affected by many operational factors. the contrary is found [74]. Al2O3 and SiO2 in the parent limestones [73]. For the bulk of the reaction when the product layer diffusion is a rate-determining step. Although calcination increases surface area and utilization of sorbents. The reaction rate is very rapid and about 45% removal is reached during the first 0. first increases to 26 wt% and then drops to 18 wt%. but isolated nuclei and crystals. alkali compounds mainly have a catalysis effect on sulfation reactions below 1200 8C. However.

the thermal conditions have great influences on SO2 reduction during coal combustion. The efficiency of 65% can also be obtained by a sorbent injection process in a 24 MW traveling grate furnace [93]. as shown in Fig. In recent years. which cannot meet the current requirements of SO2 emissions [45. A two-stage desulfurization approach that combines blending and injecting processes is proposed.1. As we know. Effect of FeCl3 on SO2 emission from coal combustion. decreased. Injecting sorbents into the combustion gas gives higher sulfur removal efficiency rather than blending sorbents with coal on the grate [91]. 8. Cr2O3 can promote the sulfation rate of CaO because of the rapid diffusion of SO2 into unreacted CaO sites through a liquid low-melting eutectic phase resulted from the reaction of Cr2O3 with CaO above 1000 8C [83]. 5. because SO2 can be both fixed by the blended sorbents in coal bed and captured by the injected sorbents in combustion gas [94. Also. It promotes the sulfur removal efficiency to about 75% during coal combustion. 7 wt% molasses pulp and 6 wt% hydration limestone gives an effective SO2 reduction in a 46. the combustion conditions in the coal bed are not conducive to efficient sulfur capture. The limestone injection process can give SO2 removal efficiency about 37% in a 20 t/h traveling grate furnace [92].86]. where the dynamic rate is the determining factor for sulfur removal. For conventional grate furnaces. respectively. [94].5 MW traveling grate furnace [88]. cannot be ignored as well as the poor contact between the gases and powder sorbents. It is reported that a SO2 reduction of 40% from the flue gas is obtained in a 4 t/h traveling grate furnace when reformed CaCO3 is added into coal briquette [89]. They are generally characterized by low capital cost and modest SO2 removal efficiency of 40 – 60%. as shown in Fig.6 and 56. It is reported that blending CaO with feed coal or injecting it directly into the combustion gas only gives a sulfur removal efficiency of 26.J. / Progress in Energy and Combustion Science 29 (2003) 381–405 391 Fig. Desulfurization processes in industrial grate furnaces Simply blending limestones with feed coal at Ca/S ¼ 2 only gives a low sulfur removal efficiency of 15 – 20% during coal combustion on grates. An industrial briquette prepared from 87 wt% hardcoal. transitional metal compounds mainly exhibit their catalysis effects on sulfation reactions below 1200 8C.95]. 7 [85. the short residence time of SO2/H2S gas in the coal bed. Coal briquettes have been shown to be effective for sulfur retention during combustion on grates. Just like alkali compounds. biobriquettes prepared from coal and biomass under high compression have been developed for clean coal combustion in small boilers and stoves. Sulfur removal technologies in industrial grate furnaces 5. More suitable conditions for sulfur capture exist immediately above the coal bed. 7. where combustion gas temperature is below 1200 8C. which is less than 1 s. Applying . Cheng et al.7%. This is mainly because of the thermal instability of sulfation products above 1200 8C and the long duration about 1 h in the coal bed.87]. Sorbent injection processes for SO2 removal are available and in continuing development. The desulfurization efficiency of biobriquettes is strongly affected by coal type and it varies in the range 25 – 67% for eight experimental coals [90].

when the molar ratio of Ca/S increases from 2 to 6. A limestone mainly composed of CaCO3 can effectively capture the SO2 gas derived from the oxidization of pyrite at 700– 800 8C. By XRD analysis. When sorbent particle size decreases from 75 to 0. For example.96]. 9. . / Progress in Energy and Combustion Science 29 (2003) 381–405 Fig. Even finer limestones only give sulfur removal efficiency about 30% [98– 101]. 9. the thermally stable Fig. particle size and composition of calcium-based sorbents only have certain effects on the sulfur removal during coal combustion on grates. the two-stage desulfurization process to a 10 t/h traveling grate furnace gives an in-furnace SO2 reduction of 75 – 77% and a total SO2 reduction of 85 – 90% after flue gas humidification in a water-film dust catcher [96. When coarse limestones with particle diameters of 1 – 3 mm are blended with feed coal at Ca/S ¼ 2. the sulfur removal efficiency increases in a narrow range of 6% [94].1 mm. As shown in Fig. Calcium carbide residue as an industrial waste is mainly composed of Ca(OH)2. a SO2 reduction in the flue gas about 24% is obtained. The ideal molar ratio of Ca/S is two and its further increase has little benefit.97]. It is favorable to prepare effective sorbents according to the nature of the sulfur in coal [102]. which is much better than that of any component [22. Influencing factors on sulfur removal in blending sorbents with coal on grates The added quantity. Cheng et al.392 J. When sorbents composed of industrial wastes are added into the fired coal. a sulfur removal efficiency of 40% is obtained in a 6 t/h traveling grate furnace [103].2. 5. a mixture of calcium carbide residue and limestone with a weight ratio of 40:60 gives a good sulfur removal efficiency of 46% at the furnace temperature of 1200 8C. but is apt to undergo severe sintering at higher temperature. calcium carbide residue gives little promotion in sulfur removal efficiency from 23 to 24% [94]. but it hardly capture the SO2 gas released at lower temperature. Effects of calcium-based sorbents on sulfur release during coal combustion. 8. Schematic of a two-stage desulfurization process in a traveling grate furnace. It can effectively capture SO2 gas derived from the oxidization of organic sulfur at 400– 500 8C.

3. cooling quench rate of the combustion gases and the sorbent properties [45]. and sulfation reactions all have certain effects on sulfur removal in furnaces [115]. molding pressure. It should be noticed that even for the same in-furnace desulfurization process. Ignition at the bottom of briquette gives a higher sulfur retention efficiency than ignition at the top. Also. it is probably more feasible to perform numerical Fig. Desulfurization processes in pulverized coal fired boilers Sorbent injection locations are critical for sulfur removal from flue gas in PCFB. The largest full-scale demonstration unit of the LIFAC process has been operated at SaskPower’s 300 MW Poplar River Power Station in Canada since 1990. ignition pattern. In general. Although its market niche is likely to be limited to smaller industrial boilers or existing boilers with . A briquette prepared under lower molding pressure with finer sorbents has a better desulfurization capability. due to the larger reducing region in the coal bed where CaS is formed as a thermally stable sulfation product [105]. temperature field. mixing of sorbent particles with SO2 gas. 6. the potential for application depends on practical factors in plants. which gives a total SO2 reduction of 70% [112. A LIFAC process (limestone injection into the furnace and activation of unreacted calcium) has been developed by the Tempella Company. Sulfur removal technologies in pulverized coal fired boilers 6. 10. residence time of sorbents in the furnace. 5. The two-stage desulfurization process in coal bed and combustion gas is competitive with regard to cost effectiveness. Several desulfurization processes have been developed and demonstrated in experimental or industrial PCFBs. In order to determine the optimal injection location that leads to the highest desulfurization efficiency. A combined process comprising furnace limestone injection. 3CaO·3Al 2 O 3 ·CaSO 4 and Ca 5 (SiO 4 ) 2 SO 4 are found in desulfurization residue derived from coal combustion on grates. it is essential to perform calculations based on calcination – sulfation models for the actual industrial conditions [108].J. in-duct humidification and bag-filter capture gives a SO2 reduction of 80% in a pilot-scale PCFB [114]. particle size and composition of sorbents have effects on the sulfur retention efficiency in coal briquettes combustion.1. It is found that the potential core length for the particle-laden jet in a sorbent injection process is nearly twice as large as that for the single-phase flow. A limestone injection multi-stage burner process (LIMB) in which limestone is added to the periphery of a ‘Low NOx’ burner typically reduces SO2 emissions by 30– 50% at Ca/S ¼ 2 [45. An upper-FSI process gives a SO2 reduction of 30 – 40% at Ca/S ¼ 2 [110]. adding some alkali or transitional metal compounds into limestone gives an increase in desulfurization efficiency during coal briquette combustion [107]. because calcium hydroxide has lower calcination temperature and scallop shell has larger porosity after calcination [106]. Recirculation of the particle-laden flow occurs downstream from the axial location where all concurrent flow is entrained into the diverging jet before the jet hits the duct wall [116]. differences in SO 2 removal efficiencies among pilot facilities probably occur due to variations in the following various parameters: temperature of the injection location. How to promote the yield of the thermally stable sulfation products is a key problem in resolving the low desulfurization efficiency on grates [94]. phases of CaSO 4 . Cheng et al. / Progress in Energy and Combustion Science 29 (2003) 381–405 393 a short residual lifespan. as shown in Fig. Owing to the great difficulties in investigating the details of sulfation course by experimental means under variable combustion conditions. Influencing factors on sulfur removal in coal briquettes combustion on grates Many factors such as coal size. It is found that calcium hydroxide and scallop shell both have better desulfurization capabilities than limestone. particle and gas concentration distribution. CaS. the ability to promote sulfur removal efficiency is very limited during coal combustion on grates. the turbulent velocity.109]. In summary. XRD analysis of desulfurization residue derived from coal combustion on grates. It is reported 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 downstream wet precipitator [111]. 10. if only chemical compositions or physical properties of sorbents are improved.113]. A large-sized coal briquette provides a longer residence time of the SO2 gas in the particles and more chance for SO2 capture by the limestone [104].

The grinding cost and destruction of pore volume. Hydration promotes the yield of calcium aluminate silicate and results in an improved microstructure.117]. in addition to other parameters such as particle size and surface area [75]. when the specific surface area of calcined limestone increases. Activation methods in preparation of reformed sorbents In order to promote reaction activities of sorbents for sulfur removal. because the formation of a thin product layer over a large surface area leads to a high conversion of the solid [126].394 J. it is effective to improve their physical properties by controlling the operational parameters in the preparation process. sintering and sulfation processes suffered by small limestone particles injected into the post-flame zone of PCFB to reduce SO2 emissions [124.3 m2/g and on the calcium content that varies in the range 6 – 748 mg/l. The sorbent utilization achievable for reaction times of practical interest increases with surface area. It is reported that introducing CO2 gas into Ca(OH)2 suspension solution produces a reformed CaCO3 with surface area of 10 – 70 m2/g.1 cm3/g [121]. it is feasible to make use of them to prepare low-cost sorbents for sulfur removal. Some distributed pore models and random pore models have been developed to analyze the simultaneous calcinations. A sintering process under limestone injection conditions results in superheater deposits. It has little effect on the pore volume that averages 1. A model based on fractal geometry suggests that the average pore radius decreases with a reduction of the fractal dimension. as shown in Fig. The plate-like pore geometry developed by some limestones and calcium hydroxides has been shown to have several advantages over the cylindrical shape. When calcium lignosulfonate or ethanol – water solution is used in the CaO hydration process. The optimum utilization is achieved when limestone is calcined to a structure with fractal dimension between 2. Effects of particle size on sulfur removal in the limestone injection process It is recognized that smaller sorbent particles give higher SO2 reduction and CaO conversion. The sulfation reaction rate of ultrafine CaO particles ðdp . It is reported that the ratio of coal ash to Ca(OH)2 have significant effects on the surface area that varies in the range 2. The sorbent surface area has a linear dependence on the ratio of coal ash to Ca(OH)2. with activation energies ranging from 20 to 27 kcal mol21 [124].4.5. It is speculated that diffusion resistance inside a particle is eliminated with particle size of 1 – 2 mm. 6. alkali and alkaline earth sulfates and chlorides in coal ash promote the fouling and slagging on hot surfaces. where CaO or partly sulfated CaO particles grow together by interactions with the flue gas. A sulfur removal efficiency of 50% can be obtained by a furnace injection process with limestone particle size of 5 – 100 mm. Furnace sorbent injection in a slurry form is found to increase sulfur removal by lessening sorbent sintering due to evaporation of the slurry droplets and by reducing sorbent particle size in the slurrying process [119].5 and 2. It is reported that pore diameters of 5– 30 nm are desirable for particles larger than 1 – 2 mm.5– 64. A decrease in limestone mean diameter from 10 to 1 mm promotes the SO2 capture from 40 to 50% at Ca/S ¼ 2 [42]. which leads to better SO2 capture [118]. Very similar product layer diffusion coefficients are obtained for calcium carbonate and for calcium hydroxides.127]. Cheng et al. eventually escaping from the furnace and being captured by the downstream dust catcher. 0:1 mmÞ is found to be 5 £ 102 2 5 £ 103 times higher than that of conventional CaO particles ðdp . local temperature and initial degree of sulfation have influences on the sintering tendency of CaO particles. Because there are some alkali and alkaline earth compounds in coal ash. in which gas composition is an important determinant.7 [125]. and further reduction in particle size gives no additional benefit [42. When air-cooled probes are inserted into the superheater area of a 500 MW PCFB with time injection in . which has higher sulfation capability than limestone [117]. as well as having important implications for particulate collection and ash handling equipments. The gas composition. hydration time and other operational parameters [120]. / Progress in Energy and Combustion Science 29 (2003) 381–405 simulations to clarify the complex gas – solid reaction mechanisms in an in-furnace sorbent injection process. 6. 1 mmÞ used in dry injection processes [122]. decide a minimum mean diameter of approximately 5 mm [6]. Fouling and slagging problems on hot surfaces in the sorbent injection process The sorbents injected into combustion gas react with SO2 as the combustion gas cools. The pyrite. the porous structure of calcium hydroxide is improved and the particle size is decreased.2. 6. 11 [123]. if sorbents are ground too fine. the pore volume located in larger pores that are greater than 5 nm contributes to a high SO2 removal and CaO conversion. 6. The key problem is to activate the effective compositions in coal ash. while in situ sulfation has some effects on deposit formation during coal combustion [128]. Effects of porosity structure on sulfur removal in the limestone injection process The particle size and pore size distribution both have important effects on high-temperature and short-time sulfation reactions. generally by a hydration process of Ca(OH)2 and coal ash under elevated pressure. This process significantly increases dust burden and may well enhance fouling and slagging on hot surfaces. producing a higher sorbent reactivity and delaying pore plugging. For superfine limestones.3.

morphology.131]. the upper furnace in order to collect samples of short-term deposits. chemical composition.7.6. cement components and so on [132. PCFB ash has many spherical particles and a much higher lime content due to the lower desulfurization efficiency. The fly ash derived from a conventional PCFB with a lime injection process and from a circulating FBC with a limestone injection process presents some similar features: fine granulometry.to high-sulfur coal. The leachates obtained from both samples are rich in soluble salts of CaSO4 and Ca(OH)2. presence of anhydrite phase and sulfate content. The hydration reactions of FBC ash are dominated by sulfate chemistry that is the formation of gypsum and ettringite. Their potential utilization is reported as road subbase. / Progress in Energy and Combustion Science 29 (2003) 381–405 395 Fig. while arsenate. Sorbent injection does tend to shift the particle size distribution towards finer particles [129]. mass loading. but arsenic and selenium are prevented from dissolving by a high lime content.5 in the EFR) [123]. Using flue gas humidification or conditioning with SO3 may bring the resistivity back to an acceptable level. Combining a downstream ceramic filtration or a flue gas dry scrubbing with a furnace injection process can improve the sulfur capture and dust collection performance in a cost effective manner [130. 6. mineralogy and behavior to water contact. brick material. such as electrical resistivity. Ca/S ¼ 1. 1CaO ¼ 0. Model simulations of the impact of particle size and pore size distribution (10008C. The fly ash and sorbent mixtures derived from a sorbent injection process contain rougher particles and tend to be more cohesive. 11. the formation of ettringite crystals stabilizes calcium and sulfate ions.133]. it is essential to evaluate their granulometry. Influence of sorbent injection processes on dust catching A high-temperature sorbent injection has some effects on particulate properties in the flue gas. 6. selenate and chromate anions are trapped in the crystals. 1000ppm SO2. Cheng et al. The FBC ash does not really harden because the lime content is too low. The particulate electrical resistivity increases substantially and the electrostatic precipitator performance degrades accordingly when a sorbent injection process is applied to a boiler burning medium. embankment. while most of the trace elements in PCFB ash show an inverse concentration-particle size dependence. The FBC ash treated via the CERCHAR process and combined with pulverized fly ash appears to make portlandite available for sulfo-pozzolanic reactions. In wetted PCFB ash.J. which result in superior performance in application as a cement substitute [135]. However. size distribution. Reutilization of in-furnace desulfurization residues In order to identify the potential disposal and utilization options for the high-volume solid residues derived from coal combustion with desulfurization processes. it is found that severe deposition is always associated with high contents of either CaSO4 or CaCO3 in the deposit [74]. 2s. The dry desulfurization by-product from a LIMB process contains substantial portions of available lime and may prove amenable as a solidifying agent with the fly ash [134]. . compared to FBC ash. morphology and cohesiveness. compared to ordinary fly ash. landfill.

The variable parameters of alternating conditions include total reaction time. as shown in Fig. SO2. On the other hand. In order to commercially popularize the in-furnace desulfurization technologies.396 J. Reducing and oxidizing atmospheres in industrial grate furnaces To meet the demand of SO2 reduction during coal combustion. In the grate-traveling direction. time fraction and composition of reducing atmosphere. not only in the height direction but also in the grate-traveling direction. ash loading and residue utilization problems. etc. which is favorable to more effective sulfur retention [98]. For a fixed-bed grate furnace ignited at the bottom. The CaS produced in a reducing atmosphere is further converted to CaSO4 or SO2 in an oxidizing atmosphere. but the thickness of the reducing layer for the bottom-ignition pattern is larger than that for the top-ignition pattern. however. 7. the O2 concentration firstly decreases and then increases. with an increase in height. Desulfurization under reducing and oxidizing atmospheres The reactions between limestones and SO2 under periodically changing oxidizing and reducing conditions in FBC boilers have been extensively studied by many authors [137 – 167]. slagging. The coal bed is ignited at the top before an estimated diagonal line where volatile matter begins to release and ignite. Phase diagram for the system composed of CaO. it is important to solve the fouling. as shown in Fig. / Progress in Energy and Combustion Science 29 (2003) 381–405 and the leached selenium concentration is reduced in wetted FBC ash [136]. 14. As shown in Fig. 12 [158]. 10211 bar) for 80 – 90% of the time. and it is ignited at the bottom after the dividing line. while the CO concentration gradually increases to some extent. CaS. As shown in Fig. it is valuable to study the distribution of gas compositions and bed temperature in grate furnaces.1. to further clarify the step-by-step courses in high-temperature sulfation reactions based on the chemical thermodynamics. It is found that the dense bed is under reducing conditions (PO2 . the CO. That is to say. There exist both oxidizing and reducing layers in the coal bed for the two ignition patterns. . Cheng et al. cycle period.1. a simple process and average efficiency. CO and CO2 in FBC. Sulfur removal under unconventional atmospheres at high temperature 7. which may be caused by a bypass of the fluidization air in bubbles and jets through the dense bed. reaching the peaks at the interface between the oxidizing and reducing layers [168]. the O2 concentration gradually decreases to nearly zero. The relative importance of the two competitive reactions depends on local temperature and atmosphere. It is necessary. reducing layer. In the coal bed of a traveling grate furnace. 15. 13. Fig. oxidizing layer and fresh fuel layer.1. 7. 12. there exist changing oxidizing and reducing atmospheres in the coal bed along the height direction. The sulfation reactions under alternating conditions follow a conversion circulation. the coal bed can be divided into four layers from bottom to top. CaSO4. The consumption of O2 gas and reducing decomposition of CaSO4 have great effects on the sulfation efficiency. the ash layer. Fig. In summary. 13 [158]. there exist various oxidizing and reducing conditions. The CO2 concentration and bed temperature first increase and then decrease. Solid phase transformations taking place when limestones are exposed to alternating oxidizing and reducing conditions in FBC. with a low cost. kinetics and thermal conditions. the turning points of the profiles of gas composition just above the coal bed correspond to the transitions of the various combustion regions in the coal bed. the sorbent injection process is competitive in controlling SO2 emissions derived from PCFB.

t . H2 and SO2 concentrations firstly increase to their peaks and then decrease [88. For the conditions studied (1127 8C .J.25 s).171]. high reactive coals may be suitable for sulfur retention as CaS [172]. retention can occur with calcium dispersed within the burning coal due to a local reducing atmosphere when carbon is present.2. under fuel-rich combustion. a staged sorbent injection process is Fig. 0 . 0 . 0. Distribution of gas compositions and coal bed temperature in the height direction. PO2 . 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 .168]. Coal moisture has a strong effect on the retention level due to the formation of H2S. The experiments and thermodynamic predictions indicate that sulfur retentions of 90% can be obtained at particle temperatures above 1227 8C even with CaS fully exposed to the flue gas. Cheng et al. 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. / Progress in Energy and Combustion Science 29 (2003) 381–405 397 effectively. 1365 8C. Distribution of gas compositions in the grate-traveling direction. For fuel-lean combustion. Based on equilibrium calculations for the coal/water/limestone/air system (50 gas-phase and 6 solid-phase chemical species).169]. . 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. 1:2 [170]. 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 semianthracites (3 to 5 £ 1026 mol cm22 s21). Fig. or (2) possible full sulfur loss for the fine CaS particles because of the high porosity of CaO product layer. 0.1. 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. T . Because the oxidation rate of CaS is slower than that of most coal chars. Schematic of a staged sorbent injection process in a PCFB. The changing oxidizing and reducing conditions in the coal bed make it possible to capture SO2 on grates more Fig. 15. 1477 8C. the oxidation results in the formation of CaO and CaSO4. 14. The CaS oxidation can lead to: (1) a possible limiting retention level due to protection afforded by the formation of a CaO–CaSO4 eutectic at T . 16.02 Mpa. 7.

2. 7. Coal combustion with O2/CO2 is promising because of its high desulfurization efficiency. while other sorbents are directly injected into the upper furnace at lower temperature of 1100– 1200 8C. 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]. Schematic of O2/CO2 coal combustion. the conversion levels attained by larger particles are much lower for the direct sulfation reaction.7– 0.8 and 1 – 1. This can be explained by minimizing sintering of CaO and plugging of reaction product CaSO4 [175]. Desulfurization under O2/CO2 conditions by flue gas recirculation A high CO2 concentration is beneficial to SO2 capture by a furnace sorbent injection process during coal combustion. the effects of particle size on the conversion curves are in quantitative agreement on a relative basis [8].5 are optimal for CaSO4-based desulfurization.2 in zone III. When the CO2 partial pressure is higher than equilibrium. as shown in Fig.0 £ 1025 m limestone diameter. 8 s one-pass residence time. 18. But it is necessary to further study the sulfation mechanisms under varying reducing and oxidizing conditions at high temperatures. which reaches about 70 – 80%. It is mainly attributed to the following factors: (1) the practical residence time of SO2 is extended and SO2 is enriched Fig.398 J. and limestone is subject to the direct sulfation reaction: CaCO3 þ 1/2O2 þ SO2 ! CaSO4 þ CO2 [176]. especially the formation and conversion of the intermediate product CaS and the final product CaSO4. as shown in Fig. It is reported that the conversion level of 53 – 62 mm Greer limestone can reach about 79% during direct sulfation for long exposure time at Fig. It is reported that increasing temperature under high CO2 concentration favors reforming the microcosmic structure of calcinated sorbents [178. It is promising to apply the staged sorbent injection process combined with air-staged combustion pattern to power station PCFBs. the staged sorbent injection process is accompanied by the air-staged combustion pattern that is employed to reinforce the high-temperature reducing atmosphere and reduce NOx emissions. In this novel process. respectively. compared to normal concentration at high temperatures and usual sulfation times [174]. Cheng et al. is enhanced to about four to six times over that of conventional pulverized coal combustion. (Ca/S) ¼ 5 and 1. .5. as shown in Figs. However. This results in much higher concentration of CO2 and SO2 in the combustion gas. which is much stronger than that on the calcined sorbent reaction.179]. This air requirement and Ca/S molar ratio of 2 – 2. the calcination of limestone is restrained. 850 8 C. which gives a sulfur removal efficiency of 40 – 50% in this case. 80% of the flue gas is extracted before the dust catcher and is recycled into the furnace near the primary air combustor. This far exceeds the maximum allowable conversion level (about 55%) when the pores of calcinated limestone are completely plugged by the product CaSO4. This process involves successive sulfur retention as an intermediate product CaS in the hightemperature reducing zone and as a final product CaSO4 in the low-temperature oxidizing zone. in addition to an extremely low NOx emission and easy CO2 recovery. With an increasing amount of O2 and cooling of the flue gas. 18 and 19. In practice. 17. It is indicated that the desulfurization efficiency in O2/CO2 pulverized coal combustion.2 oxygen-fuel stoichiometric ratio. This enhances the in-furnace desulfurization efficiency to 80 – 85%. Because the particle size is found to have a very strong influence on the rate of direct sulfation. increasing the particle size from 53 – 62 to 88– 105 mm decreases the conversion level by more than 50%. For the 88 – 105 and 297– 350 mm particles. Some sorbents are blended with feed coal and injected by primary air into the furnace at high temperature of 1500– 1600 8C. 17 [180]. 0. the conversion of CaS to CaSO4 increases and is completed at an air excess coefficient of 1. The optimal values for air excess coefficient and molar ratio Ca/S for the first desulfurization stage in zone I are. because sintering is quite mitigated during direct sulfation of limestone. / Progress in Energy and Combustion Science 29 (2003) 381–405 proposed to control emissions derived from PCFB. Effect of temperature on system desulfurization efficiency under 1. The rate of direct sulfation does not decrease as much with sulfation degree as it does CaO – SO2 sulfation. 16 [173].

The kinetic catalysis of alkali and transitional metal compounds on sulfation reactions is also important under combustion conditions. / Progress in Energy and Combustion Science 29 (2003) 381–405 399 Fig. desulfurization processes in IGF and PCFB. inside the furnace owing to the flue gas recirculation. This paper focuses on sulfur removal processes in IGF and PCFB with high flame temperatures of 1200– 1600 8C. the CO2 concentration in the flue gas reaches about 80%. sulfation and kinetic catalysis properties of the possible substitute sorbents. Although there still exist many unknowns about the desulfurization mechanism in O2/CO2 pulverized coal combustion systems. 19. crystal structures.2 oxygen-fuel stoichiometric ratio. Because current research on this new process is limited to small lab-scale furnaces. Variation of system desulfurization efficiency with residence time of particles at 1400 K under 1. 3CaO·3Al2O3·CaSO4 and Ca5(SiO4)2SO4 are thermally stable at temperatures over 1300 8C. viz. Although SrSO4. It is promising to utilize the temperature and burning gas distribution to produce CaS and a-CaSO4 phases as sulfation products in furnaces. Because the main reason for low desulfurization efficiencies in IGF and PCFB is the thermal decomposition of CaSO4 above 1200 8C. it is very promising and inspiring to further develop this novel and artful process that gives a high desulfurization efficiency of 70 – 80%. (4) the unreacted calcium in the flue gas is reutilized by recirculation. These contributions are quantitatively clarified as follows: below 1177 8C. 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. After many cycles of recirculation. the latter contributes above two-thirds to the overall increase in desulfurization efficiency [181]. a-CaSO4 is thermally stable under oxidizing conditions below 1495 8C and so is CaS under reducing conditions below 2400 8C. kinetics of sulfur retention reactions of sorbents. Installing a large humidification tower before the dust catcher. It is valuable to study further . The flue gas recirculation decreases the flame temperature. (2) CaSO4 decomposition is inhibited because of the high SO2 concentration. it is difficult to take effective measures to promote the yields of such products during coal combustion in furnaces. which also results in a lower yield of thermal NOx. thermal stabilities of sulfation products.J. (Ca/S) ¼ 5 and 1.0 £ 1025 m limestone diameter. The SO2 reduction without sorbents during coal combustion. which have much lower desulfurization efficiencies than those in fluidized bed combustors. in which sorbents are injected into the primary air field and the upper furnace to capture SO2 under reducing and oxidizing atmospheres. is promising for PCFB. Simply blending sorbents with feed coal to capture SO2 gas during combustion on grates gives desulfurization efficiency lower than 40%. It is interesting to study the chemical compositions. which can be extracted and purified by a special installation before exhaust [175]. It is proposed that the two-stage desulfurization process. Conclusions In-furnace desulfurization is a competitive technology for controlling the SO2 pollutants derived from coal combustion. SO2 is captured by sorbents both in the coal bed and in the combustion gas. In the normal Ca – S– O reaction system. it is necessary to carry out further pilot-scale and full-scale experiments to evaluate its feasibility for power station PCFBs from the technical and economic view. which also declines with an increase in furnace size and flame temperature. a LIFAC process can give an overall desulfurization efficiency about 70% after the hydrated activation of unreacted calcium. is promising for IGF. and so is the desulfurization process by flue gas recirculation under O2/CO2 conditions. due to the low capital and operating costs contrasted to flue gas desulfurization techniques. (3) the direct sulfation of limestone under high CO2 concentration. considering the short residence time and decreasing surface area of calcinated limestones at high temperature. which gives an in-furnace desulfurization efficiency over 70% and a total SO2 reduction of higher than 85% after the flue gas humidification in a water-film dust catcher. the former contributes above two-thirds. due to the low content of such reactants. and sulfur removal under unconventional atmospheres at high temperatures are reviewed. whereas above 1227 8C. Cheng et al. injecting limestones into the furnace through a low NOx burner or by a special nozzle only gives sulfur removal efficiency of 25– 50%. It is proposed that the staged desulfurization process combined with an air-staged combustion pattern. For PCFB. it is key to explore new sulfation products that are more thermally stable. 8. Burning coal briquettes with sorbents on grates or injecting sorbents into the furnace can give moderate desulfurization efficiency that are generally lower than 60%. The system desulfurization efficiency in O2/CO2 pulverized coal combustion maintains a high value over a wide range of temperatures and particle residence times. BaSO4.

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