燃料化学学报（中英文）

Adsorbent	Mn concentration w/%
Mn-40	0.26
Mn-45	0.29
Mn-50	0.32
Mn-45/F-0.2	0.28

Adsorbent	Mn concentration w/%
Mn-40	0.26
Mn-45	0.29
Mn-50	0.32
Mn-45/F-0.2	0.28

Sample	BET surface area S_BET/(m²·g⁻¹)	Total pore volume v/(cm³·g⁻¹)	Average pore size d/nm
Ca(OH)₂	18.6	0.061	0.098
Ca(OH)₂/F-0.2	17.8	0.050	1.037
Mn-45	23.7	0.097	1.082
Mn-45/F-0.2	23.6	0.087	1.083

Sample	BET surface area S_BET/(m²·g⁻¹)	Total pore volume v/(cm³·g⁻¹)	Average pore size d/nm
Ca(OH)₂	18.6	0.061	0.098
Ca(OH)₂/F-0.2	17.8	0.050	1.037
Mn-45	23.7	0.097	1.082
Mn-45/F-0.2	23.6	0.087	1.083

钙锰复合脱硫剂构筑及其SO₂/Hg⁰协同脱除研究

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刘帅鹏 ¹^,² , 李大来 ¹^,² , 任子晗 ¹^,² , 刘洁 ¹^,²^,^* , 汪黎东 ¹^,²

燃料化学学报（中英文） | 2026,54(7): 20250277-1333-20250277-1347

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燃料化学学报（中英文） 2026 , 54 (7) : 20250277-1333 -20250277-1347

钙锰复合脱硫剂构筑及其SO₂/Hg⁰协同脱除研究

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刘帅鹏¹^,², 李大来¹^,², 任子晗¹^,², 刘洁¹^,²^,^*, 汪黎东¹^,²

作者信息

¹华北电力大学燕赵电力实验室, 河北保定 071003

²华北电力大学环境科学与工程系, 河北保定 071003

通讯作者:

刘洁

Construction of calcium-manganese composite desulfurizer for synergistic removal of SO₂/Hg⁰

Shuaipeng LIU¹^,², Dalai LI¹^,², Zihan REN¹^,², Jie LIU¹^,²^,^*, Lidong WANG¹^,²

Affiliations

¹Yanzhao Electric Power Laboratory of North China Electric Power University, Baoding 071003, China

²Department of Environmental Science and Engineering, North China Electric Power University, Baoding 071003, China

Corresponding Author:

Tel: 0312-7525515, E-mail: jie.liu@ncepu.edu.cn

出版时间: 2026-07-10 doi: 10.1016/S1872-5813(26)60656-1

文章导航

摘要

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碳中和战略下，生物质锅炉成为可再生能源利用的关键设施。针对生物质锅炉烟气低浓度SO₂排放特征，钙基干法脱硫技术具有结构紧凑、基建投资少、运维简便等优势，但普遍存在脱硫剂利用率低及脱硫效率不高的瓶颈问题。本研究开发了一种基于F127表面活性剂优化分散和Mn元素掺杂氧化增效协同策略的新型Ca-Mn复合脱硫剂。Mn元素与F127的引入有效抑制了Ca(OH)₂晶粒团聚，优化了脱硫剂的孔隙结构，同时诱导了丰富氧空位结构。改性脱硫剂较大的比表面积和孔容促进了反应传质，并有效防止了脱硫产物堵塞孔隙结构、覆盖反应位点；Mn位点和氧空位构成催化中心，不仅通过促进SO₂氧化加速脱硫反应进行，同时使脱硫剂耦合Hg⁰催化氧化功能，实现了SO₂/Hg⁰的高效协同脱除。

关键词

钙锰复合材料 / 氧空位 / 干法脱硫 / 零价汞 / 协同控制

Abstract

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Under the carbon neutrality strategy, biomass boilers have emerged as key facilities for renewable energy utilization, yet are characterized by low-concentration SO₂ emissions. Ca-based dry desulfurization presents a promising technology for biomass boiler flue gas purification due to its compact structure, low capital investment and simple operation and maintenance. However, it is generally limited by the low adsorbent utilization and insufficient desulfurization efficiency. Herein, this study developed a novel Ca-Mn composite adsorbent through a synergistic strategy integrating F127 surfactant to optimize dispersion and Mn loading to enhance oxidation efficiency. The resulting adsorbent not only significantly increased the breakthrough sulfur capacity of the Ca-based material but also markedly improved the synergistic removal of Hg⁰. It was demonstrated that the introduction of Mn elements and F127 effectively suppressed the agglomeration of Ca(OH)₂ crystallites and induced an oxygen vacancy-rich structure, while simultaneously optimizing the pore structure of the adsorbent. The modified adsorbent exhibited the enlarged specific surface area and pore volume, which favored to enhance the reaction mass transfer and effectively prevent the pore blockage and coverage of active sites by desulfurization products. The Mn sites and oxygen vacancies formed catalytic centers, which not only accelerated the desulfurization reaction by promoting SO₂ oxidation but also enabled the adsorbent to couple with Hg⁰ catalytic oxidation functionality. Consequently, the simultaneous removal of SO₂ and Hg⁰ was significantly enhanced on the Ca-Mn composite adsorbent.

Key words

calcium-manganese composite / oxygen vacancy / dry desulfurization / Hg⁰ / synergistic control

引用本文

刘帅鹏, 李大来, 任子晗, 刘洁, 汪黎东. 钙锰复合脱硫剂构筑及其SO₂/Hg⁰协同脱除研究. 燃料化学学报（中英文）, 2026 , 54 (7) : 20250277-1333 -20250277-1347 . DOI: 10.1016/S1872-5813(26)60656-1

Shuaipeng LIU, Dalai LI, Zihan REN, Jie LIU, Lidong WANG. Construction of calcium-manganese composite desulfurizer for synergistic removal of SO₂/Hg⁰[J]. Journal of Fuel Chemistry and Technology, 2026 , 54 (7) : 20250277-1333 -20250277-1347 . DOI: 10.1016/S1872-5813(26)60656-1

正文

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Biomass boilers, as a key medium for biomass energy utilization, are emerging as pivotal supporting technologies for the global energy transition, offering substantial advantages such as low operating costs, high thermal efficiency, waste-to-resource conversion, and zero-carbon emission. From the perspective of flue gas pollutant control, the SO₂ emission concentration from biomass boilers is typically below 300 mg/m³, classifying it as low-sulfur flue gas^[1−2]. For low-concentration SO₂, dry desulfurization technology utilizing Ca-based adsorbents offers distinct advantages, including a compact system design, low investment costs, and ease of operation and maintenance, thus enhancing its potential competitiveness in the biomass boiler flue gas purification field^[3−4]. However, with the increasing stringency of national environmental standards, both the desulfurization efficiency of dry processes and the utilization rate of Ca-based adsorbents require further enhancement. The development of novel Ca-based materials with high specific surface areas and controllable pore structures has become a key breakthrough for enhancing the overall performance of dry desulfurization^[5−6].

Studies have demonstrated that the inadequate desulfurization performance of Ca-based materials, particularly Ca(OH)₂, is mainly due to: (1) the low intrinsic reactivity between Ca(OH)₂ and SO₂; and (2) the formation of dense CaSO₃/CaSO₄ layers on the material surface during desulfurization, which would block the reaction channels and severely hinder the mass transfer^[7−8]. To address these limitations, the modification by functional additives has emerged as a key strategy to modulate the physicochemical properties of Ca-based adsorbents and enhance their performance. For instance, Xing et al.^[9] developed a Ca(OH)₂/Al₂O₃ composite adsorbent in which the synergistic effect of high-specific-surface-area Al₂O₃ and organic surfactants substantially improved the dispersion of active Ca-based components, thereby increasing the gas-solid reaction interface area and significantly boosting desulfurization efficiency. Fan et al.^[10] and Yu et al.^[11] found that the introduction of surfactants (e.g., sodium dodecyl sulfate, ethanol, and diethylene glycol) could significantly reduce the hydration rate of CaO, which facilitated the formation of Ca(OH)₂ materials with a larger specific surface area, and consequently enhanced the saturated sulfur capacity. Furthermore, optimizing the reaction pathway of SO₂ provides an effective method to improve the desulfurization performance of calcium-based materials. Using a catalytic oxidation pre-treatment strategy, converting SO₂ to the more reactive SO₃ can substantially lower the desulfurization reaction energy barrier and increase the reaction rate. Zhong et al.^[12] modified an industrial-grade Ca(OH)₂ adsorbent by the co-loading of Fe₂O₃/MgO. Attributed to the synergistic effect of Fe₂O₃ catalysis and MgO alkaline absorption, the modified Ca-based material demonstrated markedly superior desulfurization performance compared to commercially available Ca(OH)₂. Yao et al.^[13] developed a Mn/Ce modified Ca(OH)₂ adsorbent. They observed that the Mn/Ce co-doping induced the formation of abundant oxygen vacancies within the structure of the Ca-based material, thereby enhancing its reactivity with SO₂. Similarly, Wang et al.^[14] investigated the effects of MnO₂, Fe₂O₃ and CeO₂ in promoting the desulfurization performance of Ca-based materials, and identified MnO₂ as the most effective catalyst among them.

In addition to the low-concentration SO₂ emissions, flue gas from biomass boilers tends to enrich trace heavy metal components, such as Hg, As, Pb, Cd and Cr. Among them, mercury pollutants have become a key regulated substance in the international environmental field due to their unique environmental behaviors, such as high toxicity, bioaccumulation potential, and long-range transport capacity^[15−16]. Mercury in flue gas exists in three forms: particulate-bound mercury (Hg^P), oxidized mercury (Hg²⁺), and elemental mercury (Hg⁰). Hg^P and Hg²⁺ can be effectively removed through dust removal and wet flue gas desulfurization systems, respectively. Hg⁰ generally constitutes the largest fraction of mercury in flue gas and possesses characteristics of high volatility and low water solubility. Though partial Hg⁰ can be adsorbed onto the surface of fly ash and captured by the dust removal system, or converted into Hg²⁺ via selective catalytic reduction of NO_x, its removal efficiency within the flue gas pollution control system generally remains low, thus limiting the overall efficiency of mercury control in flue gas systems^[17−18]. Therefore, the development of novel Ca-based adsorbents for the co-removal of SO₂ and Hg⁰ is of great industrial application value. However, current research on Ca-based adsorbents mainly centers on the pore structure modulation and catalytic site incorporation for enhancing desulfurization, with little consideration given to their potential for Hg⁰ co-removal and the corresponding structural control.

Based on this, this study developed a novel Ca-Mn composite adsorbent. By introducing Mn species, abundant oxygen vacancies (OVs) were constructed and acted as the active sites for catalytic oxidation of SO₂ and Hg⁰ in conjunction with the Mn sites. Meanwhile, the surfactant F127 was employed as the modifier to enhance the dispersion of Mn sites and suppress the agglomeration of Ca-based material grains, thereby optimizing the pores structure of material and the distribution of surface active sites. Based on the typical operating conditions of medium-temperature dry desulfurization systems in biomass boilers (temperature above 300 °C, relative humidity 10%−30%, NO_x concentration of (2.0−6.0)×10⁻⁴, and O₂ concentration of 4%), the simultaneous SO₂/Hg⁰ removal performance of the Ca-Mn composite adsorbent and its adaptability to varying flue gas conditions were studied. Furthermore, combining characterization techniques such as X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N₂ adsorption-desorption, and electron spin resonance (ESR), the promoting effects of the synergistic modification via Mn doping and surfactant protection on reaction mass transfer and SO₂/Hg⁰ oxidation were revealed, and the synergistic pathway between the absorption of SO₂ and the catalytic oxidation of Hg⁰ was elucidated. This study provides a new approach for the design and preparation of multifunctional Ca-based adsorbents, providing a theoretical foundation and technical insights for the development of dry cooperative control technologies targeting multi-pollutants in biomass boiler flue gas.

1　Materials and methods

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1.1　Materials

Calcium chloride (CaCl₂, analytical grade), sodium hydroxide (NaOH, analytical grade), 50% manganese nitrate solution (Mn(NO₃)₂, analytical grade), calcium lignosulfonate (C₂₀H₂₄CaO₁₀S₂, analytical grade), Pluronic F127 (average molecular weight 13000, analytical grade), and absolute ethanol (C₂H₅OH, analytical grade) were purchased from Shanghai Macklin Biochemical Technology Co., Ltd. The water used in the experiments was deionized (DI) water with the resistivity of 16 MΩ/cm.

1.2　Adsorbent preparation

Preparation of Mn-modified Ca-based adsorbent: 8.88 g of CaCl₂, 3.2 g of NaOH, varying amounts of F127 (0, 0.1, 0.2, 0.3 g), and volumes of Mn(NO₃)₂ solution (0, 40, 45, 50 μL) were mixed into 70 mL of DI water. The mixture was stirred continuously at room temperature for 30 min. The resultant product was washed with DI water and absolute ethanol until neutral pH was reached, and then dried in an oven at 60 °C for 12 h. Subsequently, the mixture was calcined in a muffle furnace at 500 °C for 4 h, with the heating rate of 10 °C/min, to obtain the precursor of the modified Ca-based adsorbent. Next, 1.5 g of the modified Ca-based adsorbent precursor and 0.03 g of C₂₀H₂₄CaO₁₀S₂ were mixed into 70 mL of DI water and stirred at room temperature for 30 min. The mixture was then transferred into a 100 mL reactor and reacted at 120 °C for 3 h. The final product was washed three times with DI water and absolute ethanol, then dried in an oven at 60 °C for 12 h to obtain the Mn-modified Ca-based adsorbent. The Mn-modified Ca-based adsorbents are labeled as Mn-x/F-y, where x represents the volume of Mn(NO₃)₂ solution used (x = 40, 45, 50 μL) and y represents the mass of F127 used (y = 0.1, 0.2, 0.3 g).

As controls, the following adsorbents were prepared: an unmodified Ca-based adsorbent without F127 surfactant or Mn doping, using a method similar to that of the Mn-modified version but without the addition of F127 and Mn(NO₃)₂ solution, labeled as Ca(OH)₂; a Ca-based adsorbent modified solely with F127 surfactant, prepared similarly but without Mn(NO₃)₂, labeled as Ca(OH)₂/F-y (where y denotes the usage of F127); and a Ca-based adsorbent modified solely with Mn, prepared similarly but without F127, labeled as Mn-x (where x denotes the volume of Mn(NO₃)₂ solution used).

1.3　Adsorbent characterizations

The Mn content in the modified Ca-based adsorbents was quantified using inductively coupled plasma optical emission spectrometry (ICP-OES, AGILENT 730). The morphology of the Ca-based adsorbents was analyzed using scanning electron microscopy (SEM, HITACHI SU8010) and transmission electron microscopy (TEM, FEI-Talos F200S). The phase structure of the samples was characterized using X-ray diffraction (XRD, Bruker D8 Advance). The surface chemical properties were examined using X-ray photoelectron spectroscopy (XPS, Thermo Fisher K-Alpha). N₂ adsorption-desorption tests were conducted using a specific surface area and porosity analyzer (Autosorb-iQ, American Konta) to investigate the physical properties of the samples. The defect structures were characterized using low-temperature electron paramagnetic resonance (ESR, Bruker A300).

1.4　Desulfurization and mercury removal performance evaluation

The desulfurization performance of the as-prepared adsorbents was assessed using a fixed-bed reactor. The adsorbent dosage was 0.3 g (0.25–0.38 mm), the inner diameter of the quartz tube reactor was 8 mm, and the simulated flue gas consisted of 4.0×10⁻⁴ SO₂, 4% O₂, with N₂ as the balance gas. The total flow rate of the simulated flue gas was 1000 mL/min, corresponding to a gas hourly space velocity (GHSV) of 26000 h⁻¹. The SO₂ concentrations at the inlet and outlet of the fixed-bed reactor were measured using a multi-component flue gas analyzer (ECOM-J2KN, Germany). The desulfurization performance was evaluated by the SO₂ removal efficiency (

$ {\eta }_{\mathrm{{S{{O}_{2}}}}} $

, %) and breakthrough sulfur capacity (S, mg/g), calculated using Equations (1) and (2), respectively. The desulfurization efficiency of 70% was established as the critical threshold, the corresponding outlet SO₂ concentration was defined as the breakthrough concentration, and the time required to reach this concentration was recorded as the breakthrough time.

$ {\eta }_{{\mathrm{S}}{{{\mathrm{O}}}_{2}}}=\frac{{C}_{0,1}-{C}_{i,1}}{{C}_{0,1}}\times 100\mathrm{\% } $

(1)

$ S=\left[{\displaystyle\sum\limits }_{i=0}^{n}\left({C}_{0,1}-{C}_{i,1}\right)\text{×}{t}_{i}\right]\text{×}\frac{Q}{m} $

(2)

where C_0,1 C_i,1 represent the SO₂ concentrations at the inlet and outlet of the fixed-bed, respectively (mg/m³), t_i is the data recording interval (2 min), Q is the flow rate of the simulated flue gas (m³/min) and m is the mass of the adsorbent (g).

During the mercury removal performance tests, the elemental mercury (Hg⁰) concentration was 70 μg/m³, the O₂ concentration was 4%, the SO₂ concentration ranged from 0 to 4.0×10⁻⁴ (when used), and the NO concentration ranged from 0 to 6.0×10⁻⁴ (when used), with N₂ as the balance gas. The total flue gas flow rate was 1000 mL/min, corresponding to a gas hourly space velocity (GHSV) of 26000 h⁻¹. A Lumex RA-915+ mercury analyzer was employed for real-time monitoring of the Hg⁰ concentration. The mercury removal capability was evaluated using the Hg⁰ removal efficiency (

$ {\eta }_{{\mathrm{H}}{{{\mathrm{g}}}^{0}}} $

, %), calculated according to Equation (3).

$ {\eta }_{{\mathrm{H}}{{{\mathrm{g}}}^{0}}}=\frac{{C}_{0,2}-{C}_{i,2}}{{C}_{0,2}}\times 100\mathrm{\% } $

(3)

where C_{0, 2}and C_{i, 2} are the Hg⁰ concentrations (μg/m³) at the inlet and outlet, respectively.

2　Results and discussion

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2.1　Characterization of adsorbent properties

2.1.1　Crystal structure of adsorbents

The concentration of Mn element in the modified Ca-based adsorbents was determined through ICP analysis. As presented in Table 1, the Mn contents in the Mn-40, Mn-45, Mn-50 and Mn-45/F-0.2 materials are 0.26%, 0.29%, 0.32% and 0.28%, respectively. The Mn concentration in the Mn-45 and Mn-45/F-0.2 samples are comparable. The crystal structure of the synthesized adsorbents was characterized using XRD. As depicted in Figure 1(a), the XRD pattern of the Ca(OH)₂ sample corresponds with the Ca(OH)₂ standard PDF card (PDF#01-076-0571), confirming the successful synthesis of a high-purity Ca(OH)₂ material. The diffraction peaks of the Mn-x adsorbents correspond to the characteristic crystal structure of Ca(OH)₂, with no diffraction signals of MnO_x phases detected, possibly due to the low concentration of Mn species. Meanwhile, with the increase of Mn doping, the intensity of the characteristic peaks of Ca(OH)₂ was decreased gradually, indicating that the incorporation of Mn resulted in lattice distortion of Ca(OH)₂, by substituting the Ca²⁺ sites or occupying the interstitial positions. Figure 1(b) compares the XRD patterns of the Ca(OH)₂, Ca(OH)₂/F-0.2, Mn-45 and Mn-45/F-0.2 adsorbents. The diffraction peaks of the Ca(OH)₂/F-0.2 and Mn-45/F-0.2 materials are consistent with the characteristic crystal structure of Ca(OH)₂. However, the introduction of Mn species and F127 template resulted in a significant decrease in the intensity of the characteristic peaks. The diffraction peak intensities of the adsorbents decreased by the order of Ca(OH)₂ > Ca(OH)₂/F-0.2 > Mn-45 > Mn-45/F-0.2. This indicates that both Mn doping and F127 introduction exhibit a significant synergistic effect in inhibiting crystal grain growth, with Mn doping exerting a stronger inhibitory effect than F127.

2.1.2　Morphology of adsorbents

Figure 2 illustrates the SEM images of the Ca-based adsorbents. As depicted in Figure 2(a), the Ca(OH)₂ sample displays an irregular microstructure, consisting of a combination of nanoparticles and bulk structures, with particle sizes ranging approximately from 0.5 to 2 μm. Figure 2(b)–(d) show that both F127 surfactant modification and Mn doping effectively optimized the microstructure of the adsorbents, resulting in similar nanoparticle structures with a relatively uniform particle size of approximately 200–300 nm, although some particle agglomeration is still visible. Figure 2(d) displays the SEM image of the Mn-45/F-0.2 adsorbent. In contrast, the synergistic modification with the F127 surfactant and Mn doping led to a more regular microstructure of the adsorbent and effectively suppressed nanoparticle agglomeration, resulting in the Ca-based adsorbent with the promoted dispersion.

Figure 3 presents the TEM and HRTEM images of the prepared adsorbents. The TEM results further confirm the smaller particle sizes and enhanced dispersion of the Mn-45/F-0.2 adsorbent. In the HRTEM images, the lattice spacings of 0.121 and 0.114 nm correspond to the (113) and (104) planes of Ca(OH)₂, respectively. Due to the low Mn doping content, characteristic lattice spacings of MnO_x species were not observed in the Mn-45 and Mn-45/F-0.2 samples. Figure 3(e) presents the elemental mapping of the Mn-45/F-0.2 sample, demonstrating the uniform distribution of Mn within the Ca-based adsorbent.

2.1.3　Physical structure of adsorbents

The physical properties of adsorbents were investigated through N₂ adsorption-desorption analysis. As shown in Figure 4(a), the Ca(OH)₂, Ca(OH)₂/F-0.2, Mn-45 and Mn-45/F-0.2 samples exhibit typical type IV adsorption isotherms with H3-type hysteresis loops, indicating that the materials are mesoporous and feature slit-shaped pores with a non-uniform pore size distribution. Moreover, the Mn-doped adsorbents, Mn-45 and Mn-45/F-0.2, demonstrate higher N₂ adsorption capacities.

Figure 4(b) illustrates the pore size distribution of the adsorbent samples, further confirming their similar mesoporous structures. The physical properties of the adsorbent samples, including specific surface area, pore volume, and pore size, are summarized in Table 2. The comparison reveals that the Ca(OH)₂ and Ca(OH)₂/F-0.2 samples exhibit similar specific surface area, pore volume, and average pore diameter, indicating that F127 does not significantly enhance the physical structure of the Ca-based material. Compared to Ca(OH)₂ and Ca(OH)₂/F-0.2, the specific surface area of the Mn-45 and Mn-45/F-0.2 samples increased to approximately 23 from 18.6 m²/g, while the pore volume and average pore diameter increased to approximately 0.09 cm³/g and 1.08 nm, respectively. This suggests that Mn doping favors to enlarge the specific surface area and optimize the pore structure of the adsorbent.

2.1.4　Surface chemical properties and defect structures of adsorbents

The chemical states of surface elements in the adsorbents were analyzed by XPS, and the results are presented in Figure 5(a)−(c). In the O 1s XPS spectra (Figure 5(a)), two characteristic peaks are observed at ~531.2 and 532.9 eV, corresponding to the O−H bonds in the hydroxyl lattice oxygen of Ca(OH)₂ and the adsorbed water molecules, respectively^[19−20]. In contrast to Ca(OH)₂ and Ca(OH)₂/F-0.2, the feature of the hydroxyl lattice oxygen in the Mn-45 and Mn-45/F-0.2 samples shifts to the higher binding energy of 531.3 eV, suggesting the successful incorporation of Mn into the crystal lattice of Ca(OH)₂. Due to the stronger electronegativity of Mn atoms compared to the Ca atoms, the Mn–O bonds are stronger than the Ca–O bonds, and therefore depletes the electron density around the surrounding O atoms, resulting in an increase in binding energy. In the Ca 2p XPS spectra (Figure 5(b)), all Ca-based adsorbents display the typical doublet structure of Ca²⁺, with characteristic peaks observed at approximately 346.8 and 350.4 eV, corresponding to the Ca 2p_3/2 and Ca 2p_1/2 orbitals, respectively^[21−22]. Notably, compared to Ca(OH)₂ and Ca(OH)₂/F-0.2, the Ca 2p doublet peaks in the Mn-45 and Mn-45/F-0.2 samples shifted to a higher binding energy by approximately 0.1 eV. The increase in Ca 2p binding energy is primarily attributed to lattice distortion effects induced by Mn doping into the Ca(OH)₂ structure. Thus, it can be concluded that Mn doping substantially alters the chemical environment and electronic structure around the O and Ca atoms in the Ca-based adsorbent^[22]. Figure 5(c) displays the Mn 2p XPS spectra of the Mn-45 and Mn-45/F-0.2 samples. Due to the low Mn content in the samples, the intensity of the Mn 2p XPS spectra is relatively low. However, XPS analysis revealed that the surface Mn concentrations of the Mn-45 and Mn-45/F-0.2 samples were 0.38% and 0.46%, respectively. This suggests that the introduction of the surfactant F127 enhances the distribution of Mn on the surface of the Ca-based adsorbent, thereby increasing the surface Mn concentration.

Furthermore, low-temperature ESR was used to examine the defect structures of the Ca-based adsorbents, with the results shown in Figure 5(d). The symmetric signal at g = 2.003 is ascribed to the unpaired electrons of oxygen vacancies (OVs) in the adsorbent, and the signal intensity corresponds to the concentration of OVs^[23]. The OVs signal on various samples decreased by the order of Mn-45/F-0.2 > Mn-45 > Ca(OH)₂/F-0.2 > Ca(OH)₂. The low-temperature ESR results indicate that the surfactant F127 inhibits particle agglomeration in Ca(OH)₂, reduces its crystallinity, and thereby promotes the formation of oxygen vacancy structures. Mn doping results in partial incorporation of Mn atoms into the Ca(OH)₂ structure, inducing lattice distortion and thereby significantly increasing the concentration of OVs in the adsorbent. The synergistic effect of F127 and Mn doping further enhances the structural defects in Ca(OH)₂, resulting in the high concentration of OVs on the Mn-45/F-0.2 sample. It is widely accepted that the OVs serve as highly efficient active sites for the adsorption and subsequent activation of gaseous O₂ molecules into highly reactive chemisorbed oxygen species via electron transfer.

These species possess a superior oxidation capacity compared to lattice oxygen, thereby significantly accelerating the oxidation reaction rate^[24−25]. During the desulfurization process, the active oxygen species rapidly oxidize adsorbed SO₂ to SO₃, which is more readily absorbed by Ca(OH)₂, thus facilitating the desulfurization reaction. Similarly, these active oxygen species can directly oxidize gaseous Hg⁰ to Hg²⁺, which is more easily captured, thereby enhancing the mercury removal performance of material.

2.2　Removal performance of SO₂ and Hg⁰ by Ca-based adsorbents

2.2.1　SO₂ removal performance of adsorbents

The performance of Ca-based materials in the dry desulfurization reaction was measured. Figure 6(a) shows the effect of Mn doping on the desulfurization performance of materials. Moderate Mn doping was found to enhance the desulfurization performance of the Ca-based adsorbent. When 45 μL of Mn(NO₃)₂ solution was added, the Ca-based adsorbent exhibited optimal desulfurization performance. No significant improvement in desulfurization performance was observed with Mn(NO₃)₂ solution additions of 40 and 50 μL. The effect of the synergistic modification of Mn doping and F127 on the desulfurization performance of the samples is shown in Figure 6(b). The study found that when 45 μL of Mn(NO₃)₂ solution was added, an optimal F127 modification of 0.2 g further enhanced the SO₂ absorption reaction. Figure 6(c), (d) present the comparison of the SO₂ breakthrough curves and breakthrough sulfur capacities of the Ca(OH)₂, Ca(OH)₂/F-0.2, Mn-45 and Mn-45/F-0.2 adsorbents. As shown, the synergistic modification with F127 surfactant and Mn doping improved the desulfurization performance of the Ca-based adsorbent. Compared to the Ca(OH)₂ sample, the SO₂ breakthrough time was extended from 50.9 to 54.5 min, and the breakthrough sulfur capacity increased from 190.2 to 205.4 mg/g. This may be due to Mn doping, combined with appropriate F127 modification, optimizing the pore structure of the adsorbent. Simultaneously, it introduces Mn active sites that enhance the desulfurization performance of the Ca-based material by promoting SO₂ oxidation.

The effects of SO₂ concentration and flue gas temperature on the desulfurization performance of the optimized Mn-45/F-0.2 adsorbent have been systematically investigated, and the results are presented in Figure 7(a), (b). The study found that with the increase of SO₂ concentration from 2.0×10⁻⁴ to 6.0×10⁻⁴, the SO₂ breakthrough time of the adsorbent decreased from 118.0 to 42.4 min. This is because high concentrations of SO₂ accelerate the coverage of active sites on the surface of adsorbent, leading to the rapid deposition of desulfurization products (CaSO₃/CaSO₄) within the pores. This leads to pore blockage and a sharp increase in internal diffusion resistance, ultimately inhibiting deeper SO₂ reactions. Within the temperature range of 300–375 °C, the reactivity of the adsorbent improved significantly by elevating the reaction temperature.

When the reaction temperature was increased from 300 to 375 °C, the SO₂ breakthrough time was extended from 24.0 to 69.0 min. This is because the increase in reaction temperature accelerates the chemical reaction rate and enhances the diffusion rate of ions through the desulfurization product layer, thereby mitigating, to some extent, the blocking effect of the product layer on the reaction^[26]. However, when the flue gas temperature was further increased to 400 °C, the reactivity of the adsorbent became similar to that at 375 °C. The reason for this is that at higher temperatures, the reaction rate between SO₂ and the Ca-based material becomes excessively rapid. The rapid formation of CaSO₃/CaSO₄ leads to increased diffusion resistance within the product layer, thereby limiting the further progression of the reaction^[27].

In addition, the effects of flue gas humidity and NO concentration on the desulfurization performance of Mn-45/F-0.2 were investigated, with the results shown in Figure 7(c), (d). The study found that a moderate level of flue gas humidity enhances the desulfurization reaction. The desulfurization efficiency of the Ca-based material was highest at a water vapor content of 20%, where the SO₂ breakthrough time increased from 50.9 min under dry flue gas conditions to 67.7 min. In contrast, at water vapor contents of 10% and 30%, the desulfurization efficiency of the Ca-based material was slightly lower than that under dry flue gas conditions. The reason is that under the appropriate humidity, a sufficiently thick liquid film forms on the surface of the adsorbent. This promotes the dissolution of SO₂ into

${\mathrm{HSO}}_3^- $

${\mathrm{SO}}_3^{2-} $

, which then diffuse through the liquid film to react with the adsorbent, forming CaSO₃/CaSO₄. In this process, water molecules act as a reaction medium, accelerating the reaction rate between ions and facilitating the desulfurization reaction^[28]. However, when the flue gas humidity is too low, the adsorbent surface cannot form an effective liquid film, leading to pore blockage. Conversely, when the flue gas humidity is excessively high, the liquid film on the adsorbent surface thickens, increasing the resistance of gas-liquid mass transfer and causing the compaction of the adsorbent particles, which in turn results in the rapid SO₂ breakthrough. The NO component in the flue gas exerts an inhibitory effect on the desulfurization reaction. When the NO concentration increased from 0 to 6.0×10⁻⁴, the SO₂ breakthrough time decreased from 50.9 to 45.3 min. This is because, in the presence of O₂, NO can be oxidized in the gas phase to form highly reactive NO₂, which then competes with SO₂ for the surface active sites on the adsorbent. Furthermore, as a highly reactive acidic substance, NO₂ preferentially reacts with the Ca(OH)₂ phase to form Ca(NO₃)₂, thereby covering the alkaline sites on the adsorbent surface and inhibiting the desulfurization reaction^[29].

Furthermore, to investigate the utilization rate of Mn-45/F-0.2 in dry desulfurization reactions, cyclic desulfurization performance tests were conducted, with the results presented in Figure 8. The study found that when the Mn-45/F-0.2 sample was applied in the second desulfurization reaction, the SO₂ breakthrough time was significantly reduced, decreasing from 54.5 min in the first reaction to 4.0 min.

This indicates that the Ca-based absorption sites in Mn-45/F-0.2 were nearly fully consumed during the initial desulfurization cycle. This characteristic is advantageous for reducing the Ca/S ratio in practical dry desulfurization applications, thereby reducing operational costs.

2.2.2　Hg⁰ removal performance of adsorbents

The Hg⁰ removal performance of the Ca(OH)₂, Ca(OH)₂/F-0.2, Mn-45 and Mn-45/F-0.2 samples was investigated. As shown in Figure 9(a), the Hg⁰ removal efficiencies for the Ca(OH)₂, Ca(OH)₂/F-0.2, Mn-45 and Mn-45/F-0.2 samples were 10.4%, 11.2%, 13.7% and 14.9%, respectively. These results emphasize the considerable potential of Ca-based adsorbents in the Hg⁰ removal and simultaneously demonstrate that synergistic modifications, including surfactant protection and Mn doping, enhance the Hg⁰ removal performance of the Ca-based material. The mechanism for the promoted performance of Mn-45/F-0.2 in the Hg⁰ removal reaction is hypothesized as follow: Mn species acting as the catalytic sites, promoting Hg⁰ oxidation through their redox cycles (e.g., Mn³⁺/Mn⁴⁺)^[30]; Mn doping inducing the formation of OVs in the Ca-based material, which facilitates the adsorption and activation of O₂ molecules, thereby accelerating Hg⁰ oxidation^[31]; and the synergistic modification through Mn doping and F127 addition, increasing the specific surface area and pore volume of the Ca-based adsorbent, thereby providing the efficient mass transfer channels for Hg⁰ diffusion. Concurrently, F127 enhances the dispersion of Mn sites, thereby improving the utilization efficiency of Mn catalytic sites and facilitating the effective contact between Hg⁰ and the active sites.

For the Mn-45/F-0.2 material, the effects of SO₂ concentration, NO concentration, and the co-presence of SO₂/NO on the Hg⁰ removal performance were investigated. As shown in Figure 9(b), (c), the acidic flue gas components SO₂ and NO exhibit distinctly different effects on Hg⁰ removal. As the SO₂ concentration increased from 0 to 5.0×10⁻⁴, the Hg⁰ removal efficiency decreased from 14.9% to 8.6%. In contrast, as the NO concentration increased from 0 to 6.0×10⁻⁴, the Hg⁰ removal efficiency increased from 14.9% to 22.5%. The inhibition of Hg⁰ removal by SO₂ primarily arises from two aspects: SO₂ competes with Hg⁰ for surface-active sites and can cause sulfation of the Mn sites, thereby blocking the catalytic oxidation of Hg⁰ at these sites^[32], and the desulfurization products (CaSO₃/CaSO₄) readily clog the pores of the calcium-based material, inhibiting both the adsorption and oxidative removal of Hg⁰. In contrast, the promotion of Hg⁰ removal by NO is attributed to the abundant OVs in the Mn-45/F-0.2 sample, which can generate surface-adsorbed oxygen species. NO is oxidized to NO₂ under the synergistic action of these surface-adsorbed oxygen species and the Mn catalytic sites. As a strong oxidant, NO₂ then oxidizes Hg⁰ to Hg²⁺, thereby enhancing the Hg⁰ removal efficiency^[33−34]. Figure 9(d) compares the Hg⁰ removal performance of the Mn-45/F-0.2 material under conditions of SO₂ alone, NO alone, and the co-presence of SO₂/NO. The study found that in flue gas environments where SO₂ and NO coexist, the inhibitory effect of SO₂ on Hg⁰ removal can be significantly mitigated. When both SO₂ and NO concentrations were 4.0×10⁻⁴, the Hg⁰ removal efficiency of the Mn-45/F-0.2 material reached 15.5%, demonstrating its potential applicability for the cooperative control of SO₂ and Hg⁰ in biomass boiler flue gas. However, compared to highly efficient Mn-based Hg⁰ removal catalysts, the Hg⁰ removal performance of the Mn-45/F-0.2 adsorbent remains relatively low. This is primarily attributed to the fact that its material design is still fundamentally oriented towards desulfurization. The main component, Ca(OH)₂, is a typical alkali absorbent that lacks favorable redox properties, making it difficult to provide an effective reaction environment required for the highly efficient catalytic oxidation of Hg⁰. In follow-up research, introducing typical catalyst support materials for Hg⁰ oxidation (such as TiO₂, Al₂O₃, etc.) to modify the Ca-based adsorbent through composite design could be considered. This would help create a more suitable catalytic microenvironment for the Mn species, thereby enhancing their promotional effect in the catalytic oxidation of Hg⁰.

2.3　Reaction mechanism of SO₂/Hg⁰ synergistic control by the Ca-Mn composite adsorbent

To investigate the synergistic removal mechanism of SO₂/Hg⁰ by Ca-based materials, XRD characterization was conducted on the Ca(OH)₂/F-0.2 and Mn-45/F-0.2 samples before and after reaction. Figure 10(a) compares the XRD patterns of the Ca(OH)₂/F-0.2 and Mn-45/F-0.2 samples after SO₂ breakthrough in the desulfurization reaction. It can be observed that after SO₂ breakthrough, the composition of both the Ca(OH)₂/F-0.2 and Mn-45/F-0.2 samples transformed from Ca(OH)₂ into the desulfurization products CaSO₃/CaSO₄ and the dehydration product CaO. Notably, the diffraction peak intensity of CaO on the Mn-45/F-0.2 sample is slightly lower than that on the Ca(OH)₂/F-0.2 sample, indicating that Mn doping modification improved the utilization rate of the Ca(OH)₂ component during the desulfurization reaction. Figure 10(b) displays the XRD patterns of the Ca-based materials after 12 h of the desulfurization reaction. Compared to Ca(OH)₂/F-0.2, the diffraction peaks for CaSO₃, CaSO₄ and CaO on the Mn-45/F-0.2 sample are stronger and sharper. This suggests that the Mn doping, which optimized the physical structure (specific surface area and pore structure) of adsorbent and accelerated SO₂ oxidation, significantly promoted the absorption of SO₂/SO₃ by Ca(OH)₂. Meanwhile, the dense CaSO₃/CaSO₄ product layer hindered the mass transfer, limiting the further reaction between SO₂ and the deeper Ca-based species. Under the catalysis of Mn sites, Ca(OH)₂ was more readily and thoroughly converted into crystalline CaO, which accounts for the significant enhancement of the characteristic CaO diffraction peaks. Figure 10(c) presents the XRD patterns of the Ca-based materials after 12 h of Hg⁰ removal reaction. Both the Ca(OH)₂/F-0.2 and Mn-45/F-0.2 samples primarily consist of CaO species. However, Ca(OH)₂ characteristic peaks of certain intensity were detected on the Ca(OH)₂/F-0.2 sample, indicating that the presence of Mn sites promoted the dehydration of Ca(OH)₂ under high-temperature conditions. Due to the low concentration of Hg⁰ in the flue gas, no characteristic peaks of Hg-containing species were detected on the surface of either sample. Figure 10(d) shows the XRD patterns of the Ca-based materials after 12 h of simultaneous SO₂/Hg⁰ removal reaction. The results are similar to those in Figure 10(b), suggesting that the co-presence of SO₂ and Hg⁰ did not significantly affect the progression of the desulfurization reaction or the composition of the desulfurization products.

The XPS results for the Ca(OH)₂/F-0.2 and Mn-45/F-0.2 samples following the reaction are presented in Figure 11. Figure 11(a) presents the S 2p XPS spectra of the samples following SO₂ breakthrough in the desulfurization reaction. In the spectra, the characteristic peaks at 167.1 and 168.4 eV are attributed to the S 2p_3/2 and S 2p_1/2 orbitals of

${\mathrm{SO}}_3^{2-} $

species, while the peaks at 169.1 and 170.3 eV correspond to the S 2p_3/2 and S 2p_1/2 orbitals of

${\mathrm{SO}}_4^{2-} $

species^[35−36].

Calculations based on the characteristic peak areas indicate that after SO₂ breakthrough, the surface concentration of

${\mathrm{SO}}_4^{2-} $

on the Mn-45/F-0.2 sample (19.7%) was significantly higher than that on the Ca(OH)₂/F-0.2 sample (12.9%). This suggests that Mn modification effectively promoted the oxidation of SO₂ to SO₃, thereby facilitating the absorption of SO₂ by the Ca-based material, enhancing its desulfurization efficiency, and increasing the accumulation of surface sulfate products. As shown in Figure 11(b)，the S 2p XPS spectra of the samples after 12 h of the desulfurization reaction are presented. Compared to Figure 11(a), the surface concentration of

${\mathrm{SO}}_4^{2-} $

on both samples increased significantly to approximately 34%. This phenomenon suggests that with the extension of the desulfurization reaction time, the sulfite products formed on the surface of the adsorbent are gradually oxidized and converted into sulfate products. Combined with the results from Figure 11(a), the primary role of Mn modification lies in promoting the initial oxidation stage of SO₂ to SO₃, while its catalytic effect on the subsequent oxidation reaction from sulfite to sulfate is not significant. Figure 11(c) presents the S 2p XPS spectra of the samples after 12 h of simultaneous desulfurization and Hg⁰ removal. The spectra are similar to those in Figure 11(b), suggesting that the presence of Hg⁰ did not significantly affect the desulfurization reaction process or the composition of products on the adsorbent surface. Figure 11(d) presents the Hg 4f XPS spectra of the samples after 12 h of Hg⁰ removal and after 12 h of simultaneous SO₂/Hg⁰ removal. However, due to the low concentration of mercury species on the sample surfaces, the obtained XPS signals are weak.

Additionally, the Mn 2p XPS spectra of the Mn-45/F-0.2 sample were compared before and after 12 h of simultaneous SO₂/Hg⁰ removal. As depicted in Figure 11(e), a following the reaction, the Mn 2p characteristic peaks shifted to higher binding energy, suggesting a decrease in electron cloud density around the Mn atoms and an increase in the oxidation state of Mn. Peak deconvolution of the high-resolution Mn 2p spectra revealed that the molar percentages of surface Mn³⁺ and Mn⁴⁺ species in the fresh sample were 56.1% and 43.9%, respectively. After the reaction, the percentage of Mn³⁺ decreased to 44.8%, while that of Mn⁴⁺ increased to 55.2%. In catalytic oxidation reactions, Mn⁴⁺ species in Mn-based catalysts are generally regarded as highly active catalytic sites, while a suitable proportion of Mn³⁺ species also facilitates the oxidation process. This is because the concentration of OVs is positively correlated with the Mn³⁺ content. Furthermore, the Mn³⁺–O bond is relatively longer and weaker, facilitating oxygen atom dissociation and allowing lattice oxygen to effectively participate in oxidation reactions^[37−39]. Therefore, the decrease in the proportion of Mn³⁺ observed in Figure 11(e) after the reaction suggests that Mn³⁺, Mn⁴⁺ and OVs collectively acted as catalytic sites in the oxidation reactions of SO₂ and Hg⁰. Additionally, the redox cycle between Mn³⁺ and Mn⁴⁺ ensures the continuous progression of the catalytic oxidation reactions.

Based on the experimental results, the mechanism of dry desulfurization and synergistic Hg⁰ control by the developed Ca-Mn composite adsorbent, Mn-45/F-0.2, is illustrated in Figure 12. During the preparation of the adsorbent, the introduction of the surfactant F127 effectively prevented the agglomeration of Ca(OH)₂ particles and promoted the uniform distribution of Mn within the calcium-based material. Mn doping resulted in the incorporation of partial Mn atoms into the Ca(OH)₂ crystal lattice, which not only suppressed the crystalline growth of Ca(OH)₂ but also optimized the pore structure of the adsorbent. This process enhanced the lattice distortion and induced the formation of abundant OVs. The Mn sites and adjacent OVs collectively form the active centers, which significantly enhance the oxidative capacity of the adsorbent. This promotes the rapid oxidation of SO₂ to SO₃, enabling its efficient absorption by the Ca(OH)₂ component, while simultaneously catalyzing the oxidation of Hg⁰ to Hg²⁺ species, thus achieving the synergistic removal of SO₂/Hg⁰. Additionally, the relatively large specific surface area and pore volume of Mn-45/F-0.2 significantly enhance the mass transfer of both SO₂ and Hg⁰ to the active sites. This not only facilitates their contact with the active centers but also effectively mitigates the blockage of the pore structure by desulfurization products during the reaction. As a result, this leads to an extended SO₂ breakthrough time and enhanced Hg⁰ removal efficiency.

3　Conclusions

收起

This study successfully developed a highly active Ca-Mn composite adsorbent, Mn-45/F-0.2, utilizing a synergistic modification strategy involving optimized dispersion with the F127 surfactant and enhanced oxidation through Mn doping. The material was subsequently employed in synergistic dry desulfurization and Hg⁰ removal. The results indicated that, compared with unmodified Ca(OH)₂, the Mn-45/F-0.2 material exhibited an extended SO₂ breakthrough time from 50.9 to 54.5 min, an increased sulfur breakthrough capacity from 190.2 to 205.4 mg/g, and an improved Hg⁰ co-removal efficiency from 10.4% to 14.9%. Characterization results revealed that Mn doping significantly suppressed the rapid crystallization and agglomeration of Ca(OH)₂ particles, enhanced the defect structure of the adsorbent, and simultaneously optimized its pore architecture, resulting in an increase in specific surface area and pore volume. F127 modification, in contrast, facilitated the uniform distribution of Mn in the Ca-based matrix and increased the surface concentration of Mn active sites. In the SO₂/Hg⁰ synergistic removal reaction, Mn sites along with adjacent OVs, form the active centers that significantly enhance the oxidative capability of the adsorbent. This promotes the rapid oxidation of SO₂ to SO₃, which could be efficiently captured by the Ca(OH)₂ component, and simultaneously catalyzing the oxidation of Hg⁰ to Hg²⁺ species. Moreover, the relatively large specific surface area and pore volume of Mn-45/F-0.2 enhance reaction mass transfer, accelerating the absorption of SO₂/SO₃ by the Ca-based material. This also effectively reduces pore blockage by desulfurization products, thereby extending the SO₂ breakthrough time and enhancing Hg⁰ removal efficiency. This study provides experimental data and theoretical support for the modification technology of dry calcium-based adsorbents using the Ca-Mn composite adsorbent, offering valuable guidance for achieving efficient and cost-effective removal of low-concentration SO₂/Hg⁰.

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doi: 10.1016/S1872-5813(26)60656-1

接收时间：2025-10-11
首发时间：2026-09-23
出版时间：2026-07-10

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收稿日期：2025-10-11
修回日期：2025-12-01
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¹华北电力大学燕赵电力实验室, 河北保定 071003

²华北电力大学环境科学与工程系, 河北保定 071003

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科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
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