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Article

Selection of High-Performance Sorbent for H2S Removal and Regulation of Reaction Products via Thermodynamic Simulation

by
Yanni Xuan
1,
Shuaicheng Peng
1,
Hong Tian
1,*,
Zhangmao Hu
1,
Yanshan Yin
1 and
Haitao Gao
2,*
1
School of Energy and Power Engineering, Changsha University of Science and Technology, Changsha 410114, China
2
State Key Laboratory of Precision Manufacturing for Extreme Service Performance, Central South University, Changsha 410083, China
*
Authors to whom correspondence should be addressed.
Materials 2025, 18(12), 2918; https://doi.org/10.3390/ma18122918
Submission received: 29 April 2025 / Revised: 12 June 2025 / Accepted: 16 June 2025 / Published: 19 June 2025
(This article belongs to the Section Materials Physics)
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Abstract

:
Thermodynamic simulations of the H2S removal from blast furnace gas by metal oxides were conducted to select a suitable metal desulfurizer. Notably, the Mn oxides demonstrated themselves as the optimal H2S removal agents. They are characterized by the absence of radioactive pollution, high cost-effectiveness, high sulfur fixation potential, and non-reactivity with CO2, CO, and CH4. Through a comprehensive comparison of Mn oxides, the sulfur fixation potential and sulfur capacity were elucidated as follows: Mn3O4 > Mn2O3 > MnO2 > MnO. The higher-valence manganese oxides were shown to have stronger oxidation ability, larger sulfur capacity, and the advantage of producing elemental sulfur with high utilization value during the reaction. After selecting Mn oxides as the optimal H2S removal agents, an equilibrium component analysis of the regeneration process of the sulfided MnS was carried out. The results indicate that an oxygen amount that is 1.5 times that of MnS is the optimal dosage, and such an amount can oxidize all of the MnS at a relatively low temperature. Conversely, a diluted oxygen concentration can further reduce the temperature of the regeneration process, preventing the sintering of the regenerated desulfurizer and thus maintaining its reusability. This research provides a sufficient theoretical basis for the use of Mn oxides as active components of desulfurizers to remove H2S from blast furnace gas and for the regeneration of MnS after desulfurization.

1. Introduction

As a foundational pillar of the global economy, the steel industry contributed 1.89 billion tons to global crude steel production in 2023 [1,2,3]. The production process generates 1700~2500 m3 of blast furnace gas (BFG) per ton of steel [4], which translates to a substantial volume of byproduct gas requiring safe and efficient utilization. BFG, a byproduct of steel manufacturing processes, contains hydrogen, methane, and carbon monoxide [5], endowing it with significant energy utilization potential and establishing it as the primary fuel source for industrial furnaces, such as hot blast stoves and reheating furnaces [6,7,8].
However, H2S and other impurities not only corrode transmission pipelines, but also generate polluting gases (e.g., SO2) during combustion [9,10]. These contaminants severely endanger human health, environmental integrity, and industrial infrastructure, thereby impeding the efficient utilization of gaseous resources [11]. Therefore, the concentration of H2S should be limited at very low levels on various occasions [12,13]. For example, the acceptable environmental thresholds for H2S have been stipulated as 0.02–0.1 ppm [14]. To comply with increasingly rigorous emission regulations (i.e., EU BREF), advanced BFG treatment becomes critical for achieving energy conservation and emission reduction objectives [15,16].
Current H2S deep removal strategies primarily comprise adsorption [17], absorption [18], catalytic oxidation [19], and biological treatment [20]. Among these, adsorption desulfurization has emerged as the most promising technology due to its high-efficiency deep H2S removal capacity [21], encompassing activated carbon adsorption [22,23], microcrystalline material adsorption [24], and metal oxide adsorption [25,26,27]. Compared with activated carbon adsorption that requires continuous oxygen supplementation [28] and microcrystalline methods suffering from high implementation costs [29], metal oxide adsorption offers advantages, such as high sulfur removal efficiency and excellent selectivity [30]. Notably, the elemental sulfur generated during the process can be recycled for industrial applications, thereby promoting circular economy practices and being recognized by the international academic community as a highly viable technical pathway [31]. The development of high-efficiency desulfurizers and optimization of regeneration protocols are of profound significance for enhancing BFG utilization efficiency and advancing energy-saving and emission-reduction initiatives in the global steel industry [32,33].

2. H2S Removal and Regeneration Process by Metal Oxides

The H2S desulfurization and metal oxide regeneration process is schematically depicted in Figure 1. Initially, the metal oxide undergoes a reaction with the H2S present in BFG, yielding sulfide and water. Subsequently, oxygen introduction facilitates the oxidative regeneration of sulfide back to metal oxide, with SO2 concurrently produced as a byproduct.
Extensive investigations have been conducted on Fe-, Cu-, Ca-, and Zn-based, as well as composite, metal oxides as desulfurization sorbents for H2S abatement. Zhan et al. [30] reported α-Fe2O3 synthesis via MIL-101 (Fe) calcination at 500 °C, achieving H2S oxidation to sulfur and sulfate. However, this iron-based sorbent suffers from sintering issues under high-temperature conditions. In contrast, Wu et al. [34] introduced a microwave sulfidation protocol using activated carbon-supported Fe2O3, demonstrating optimal performance at 600 °C. Rezaei et al. [35] fabricated titanium silicate-supported CuO via ion exchange, which exhibited enhanced porosity and achieved sub-0.5 ppm desulfurization precision. Li et al. [8] developed a Cu-K-Co/AC catalyst through impregnation for simultaneous COS and H2S removal. Their results showed sulfur capacities of 90.59 mg/g for COS and 127.62 mg/g for H2S under 60 °C and 0.1 vol% O2. Mechanistic studies revealed that KOH-provided basic sites facilitated COS hydrolysis to H2S, while CuO/Cu2O lattice oxygen promoted H2S oxidation to elemental sulfur. Notwithstanding, sulfate accumulation was identified as the primary deactivation mechanism. Oh et al. [36] immobilized ZnO nanostructures (ZnO-nR vs. ZnO-nS) on cordierite–mullite supports via seed growth, demonstrating ZnO-nS superiority with 48.7 mg/g sulfur capacity and 75.4 min breakthrough time at 400 °C. This performance was attributed to improved surface coverage and crystallinity. Significantly, ZnO-nS retained 95% of its initial capacity after five regeneration cycles, indicating favorable mass transfer properties. Feng et al. [37] compared ZnO synthesis methods (room temperature solid-phase method vs. homogeneous precipitation method), revealing that the latter produced sorbents with superior textural properties (40.81 m2/g surface area vs. 33.20 m2/g) and regeneration efficiency. However, Zn volatility remained a critical limitation. Conversely, CaO-based sorbents [38] have been shown to exhibit thermal stability up to 1200 °C with reversible O2 regeneration capability. Li et al. [39] optimized MnₓOᵧ/Al2O3 via calcination parameters, identifying 900 °C/6 h treatment as optimal for maintaining 85 mg/g sulfur capacity over five cycles.
Composite metal oxides have emerged as promising alternatives. Cimino et al. [40] reported Cu0.5Zn0.5/Al5 composite oxides with 26.2 mg/g sulfur capacity (9× improvement over unmodified γ-Al2O3). Min et al. [25] demonstrated that Fe-Cu synergy in Fe-Cu/SBA-15 composites enhanced H2S adsorption through basic environment formation, achieving 74.08 mg/g capacity. Sánchez-Hervás et al. [41] developed ZnO-NiO/rGO composites, achieving complete 9000 ppmv H2S removal at 400 °C under industrially relevant conditions. The rGO matrix improved metal oxide dispersion (99.35 m2/g) and sulfidation selectivity. Kim et al. [42] synthesized coral-like Mn2O3/Fe2O3 nanocomposites, demonstrating 11.97 mg/g room-temperature capacity—4.8× higher than α-Fe2O3.
Notwithstanding these advancements, existing literature lacks systematic thermodynamic screening of metal oxides and precise regeneration product distribution control. This study addressed these gaps by implementing computational thermodynamic modeling to systematically evaluate periodic table metal oxides and to provide theoretical guidance for optimizing regeneration product distributions.

3. Thermodynamic Analysis

Notably, the selection of metal oxides as active components in H2S adsorbents is of paramount importance. In previous research [43], a systematic screening of metal oxides as active components for SO2 removal from flue gas was conducted via thermodynamic methods. Manganese oxides have been identified to exhibit high desulfurization activity across a broad temperature range, and their desulfurization performance remains unaffected by other gas components in flue gas. Notably, the MnSO4 generated during desulfurization can be regenerated into manganese oxides using H2, enabling cyclic utilization of the desulfurizer and recovering substantial sulfur crystals. Subsequent experiments [44] have confirmed that manganese-based metal oxides exhibit superior efficiency and sulfur capacity for flue gas desulfurization compared to other sorbents, with the desulfurization efficiency of the sorbent being significantly enhanced and the operational cost of desulfurizers for enterprises reduced accordingly.
Ideal candidates must exhibit high sulfur-fixation capacity, rapid reaction, robust mechanical stability, negligible side-reactions, and cost-effectiveness [45,46,47]. Therefore, prior to the experimental validation of H2S removal from blast furnace gas using metal-oxide-based desulfurizers, thermodynamic analysis was conducted to evaluate the potential candidates. Gibbs free energy serves as a critical parameter for determining reaction spontaneity and feasibility. For a generic reaction, the Gibbs free energy change (ΔG) was calculated via Equation (1):
Δ G = − R T lnK + R T lnQ
The spontaneity of chemical reactions is governed by the Gibbs free energy change: ΔG < 0 denotes spontaneous forward progression, ΔG > 0 signifies non-spontaneity, and ΔG = 0 corresponds to equilibrium states [48]. Notably, temperature emerges as a critical variable in thermodynamic evaluations, and it is capable of reversing reaction spontaneity through thermal modulation.
HSC Chemistry (developed by Outotec, Finland) is a preeminent thermodynamic and chemical equilibrium simulation platform in process engineering and materials science. It is integrated with a thermochemical database encompassing over 28,000 compounds and advanced computational algorithms, which enables the prediction of reaction feasibility, phase equilibria, and energy requirements under user-defined conditions [49,50]. Key functionalities encompass the following: (1) calculation of Gibbs free energy (ΔG), enthalpy (ΔH), entropy (ΔS), and heat capacity (Cp) for chemical reactions; (2) equilibrium analysis for gaseous, liquid, solid, and aqueous systems; and (3) process simulation, involving optimization of temperature, pressure, and reactant stoichiometry. Notably, software was utilized to conduct comprehensive thermodynamic investigations on metal oxides. Westmoreland and Harrison [51] elucidated the thermodynamic behavior of H2S adsorption on the oxides of Cu, Zn, Fe, V, Mn, Ca, Mo, W, and Co. Abdalla et al. [52] investigated copper-based oxygen carriers for chemical looping air separation (CLAS) oxygen production. HSC software (v6.0) was employed to perform thermodynamic evaluations, identifying optimal conditions for oxygen generation and carrier oxidation while simulating oxygen equilibrium partial pressure. Lopez Ortiz et al. [53] utilized HSC software for thermodynamic modeling to determine the optimal reaction temperature between cobalt tungstate and methane. Jerndal et al. [54] utilized HSC software to perform thermal analysis, modeling the reactions of multiple oxygen carriers in chemical looping combustion. Their results demonstrated complete fuel gas conversion over copper, manganese, and iron oxides. Xuan et al. [43] employed HSC software for the thermodynamic modeling of a flue gas desulfurization (FGD) system, identifying manganese-based oxides as the optimal active components for chemical looping desulfurization. These materials exhibit distinct advantages, including environmental benignity, sintering resistance, and cost-effectiveness, alongside high sulfur-fixation capacity; chemical inertness toward CO2, H2O, and CO; and enhanced SO2 removal.
The Reaction Equation and Equilibrium Composition modules of HSC Chemistry 6.0 were employed to systematically investigate the thermodynamic behaviors of the H2S removal and desulfurizer regeneration processes. Using the Reaction Equation module, the Gibbs free energy changes in reactions at varying temperatures were calculated to evaluate the thermodynamic feasibility of H2S removal from blast furnace gas by various metal oxide desulfurizers. The Equilibrium Composition module was utilized to calculate reaction products under diverse operating conditions for both desulfurization and regeneration processes, thereby elucidating the dominant reaction mechanisms and optimizing process parameters [55]. This study systematically evaluated the reactivity of metal oxides with blast furnace gas components, leveraging thermodynamic principles. Notably, blast furnace gas [56] contains not only major constituents (CO, CO2, N2, H2, O2, and CH4), but also trace sulfur compounds (H2S and COS), which are quantified in Table 1. A total of 22 candidate metal oxides were selected from the periodic table, excluding radioactive, low-melting, or prohibitively expensive metals. The final set included Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Sb, Nb, Mo, Ta, W, Hf, Mg, Ca, Sr, Ba, and Cd.

4. Results and Discussion

The selected temperature range of 100–1000 °C encompasses the operational spectrum of blast furnace gas from generation to utilization, comprising the medium–low temperature fraction of blast furnace gas post-waste heat recovery and the high-temperature fraction of unpurified, uncooled hot coal gas [57,58,59,60,61,62]. The temperature range for H2S removal by metal oxides was established as follows: Desulfurization temperatures for H2S removal from BFG using metal oxide sorbents are contingent upon the specific sorbent chemistry, typically spanning a broad thermal regime. The temperatures at which metal oxide desulfurizers remove H2S from BFG vary with the type of desulfurizer, typically spanning a broad temperature interval. For instance, iron-based sorbents demonstrate optimal desulfurization efficiency at 100–200 °C, whereas zinc- and manganese-based materials are preferentially deployed within the 200–600 °C range [58,59]. Garces et al. [60] reported that commercial ZnO exhibits a direct correlation between sulfidation temperature (60–400 °C) and sorbent breakthrough time. Li et al. [61] experimentally evaluated Zn-Mn oxides supported on γ-Al2O3 as sorbents for H2S removal within the 350–600 °C range. The results demonstrated that 10 wt% Zn-Mn/γ-Al2O3 composites achieve a notable H2S adsorption capacity of 52 mg S/g-sorbent at 600 °C. At ultra-high temperatures (600–1000 °C), specialized treatment protocols are requisite to preserve sorbent stability [62]. The thermal tolerance of the desulfurization systems was established as follows: Fixed-bed reactors employing metal oxide sorbents are engineered to withstand operational temperatures ≤ 1000 °C [63]. Collectively, the 100–1000 °C temperature envelope encompasses the entirety of BFG processing stages, the optimal performance windows of metal oxide sorbents, and the thermal limits of infrastructure, thereby establishing a comprehensive operational framework.

4.1. Fixing-Sulfur Potentiality

For the fixing-sulfur potentiality of the metal oxides, the Fe, Ni, Cu, Zn, Sb, Mo, W, Ca, Sr, Ba, Cd, V, Mn, and Co oxides must have excellent characteristics of active components in the desulfurizer, which is consistent with previous studies. Manganese oxides (MnOX) have received special emphasis as an absorbent for element sulfur recovery. Fang et al. [64] investigated the H2S removal performance of activated carbon (AC) supported with various metal oxides. Their study revealed that the H2S removal efficiencies of the as-prepared catalysts followed a descending order: Mn/AC > Cu/AC > Fe/AC > Ce/AC > Co/AC > V/AC. Copper oxide (CuO) adsorbent has been extensively investigated as a promising candidate owing to its favorable thermodynamic properties and high H2S removal capacity. Wang et al. [65] evaluated the performance of three-dimensionally ordered macroporous (3DOM) CuO adsorbents for H2S removal at ambient temperature. The results demonstrated that the CuO adsorbents achieved a desulfurization efficiency exceeding 99% and a breakthrough sulfur capacity of 137 mg/g-adsorbent. Iron oxides derived from mining residues are regarded as promising adsorbents for H2S removal. Cristiano et al. [66] investigated the adsorption performance of nanostructured iron oxide (NIO) toward H2S at room temperature, whereby 100% removal efficiency was achieved and sustained for 5.6 h. Magnesium oxide (MgO) and zinc oxide (ZnO) sorbents are also reported in many flue gas desulfurization systems, which has prompted researchers to view them as promising adsorbents. Yang et al. [27] investigated the H2S removal capacities of MgO, ZnO, and composite MgₓZn1-X/AC adsorbents at ambient temperature. The results demonstrated that the sulfur capacities of monometallic MgO and ZnO were both inferior to those of the composite counterparts. Table 2 summarizes the desulfurization performance and cost [67] of common metal oxides for flue gas desulfurization. Evidently, the Mn oxides exhibited the lowest cost but highest sulfur capacity.
Metal oxides react with H2S via two distinct pathways, as shown in Equations (2) and (3) [68]:
MO + H 2 S → MS + H 2 O ,
MO + H 2 S → MS + H 2 O + S
where M denotes a metallic element.
The sulfur-containing reaction products include sulfides (MS) and elemental sulfur (S). Gibbs free energy calculations were performed to evaluate the sulfur-fixation capacity of the candidate metal oxides. Figure 2 illustrates the ΔG profiles for H2S reactions with 22 metal oxides. Notably, Figure 2a reveals that the Al, Ti, Cr, Zr, Hf, and Mg oxides exhibited positive ΔG values across the 100~1000 °C range, indicating thermodynamic infeasibility for H2S removal. Conversely, the Fe, Ni, Cu, Zn, Sb, Mo, Ca, Sr, Ba, Cd, and Co oxides demonstrated negative ΔG values, signifying spontaneous reactivity with H2S under these conditions. WO3 displayed temperature-dependent behavior, with spontaneous reactions occurring between 100~800 °C. The results presented in Figure 2b indicate that the Nb and Ta oxides exhibited positive ΔG values for the H2S reactions across the 100~1000 °C range, whereas the V and Mn oxides demonstrated negative ΔG values, signifying spontaneous reactivity under these conditions.
Collectively, the Al, Ti, Cr, Zr, Hf, Mg, Nb, and Ta oxides were excluded from active component selection due to their lack of reactivity with H2S. In contrast, the Fe, Ni, Cu, Zn, Sb, Mo, W, Ca, Sr, Ba, Cd, V, Mn, and Co oxides emerged as promising candidates for H2S removal applications.

4.2. Reacting with CO and CO2

During the desulfurization processes, metal oxides may undergo reduction reactions with CO, generating trace metallic species that reduce oxide loading and impair H2S removal reactivity [69,70]. Thermodynamic spontaneity dictates that reactions proceed in the forward direction when ΔG < 0. Figure 3a reveals that the Fe, Ni, Cu, Sb, Mo, W, Cd, and Co oxides exhibited spontaneous CO interactions within the 100~1000 °C range, forming dissociative metallic phases that compromised the desulfurizer performance. Conversely, the Zn, Ca, Sr, Ba, V, and Mn oxides maintained positive ΔG values for CO reactions, indicating chemical inertness toward CO. These findings justified the exclusion of Fe, Ni, Cu, Sb, Mo, W, Cd, and Co oxides from active component selection.
CO2 ranked as the third most abundant constituent in the blast furnace gas, necessitating evaluation of its interaction with the metal oxides. During desulfurization, metal oxides may adsorb CO2 in addition to H2S, forming carbonates that induce irreversible deactivation of active sites [71,72,73].
Figure 3b illustrates the ΔG profiles for CO2 reactions with eight metal oxides. The Sb, Mo, W, V, Mn, and Co oxides were excluded from the analysis due to their chemical inertness toward CO2. Notably, the Sr and Ba oxides exhibited negative ΔG values across the 100~1000 °C range, while CaO and CdO demonstrated temperature-specific reactivity (100 °C~900 °C and 100~300 °C, respectively). These spontaneous carbonate-forming reactions compromised the H2S removal efficiency, leading to their elimination from active component selection. Conversely, CuO maintained positive ΔG values, indicating thermodynamic stability against CO2. For the Fe, Ni, Zn, and Cd oxides, ΔG increased with temperature, shifting the following reaction spontaneity thresholds: NiO and ZnO showed initial negative ΔG near 100 °C, FeO between 100~150 °C, and CdO between 100~250 °C before becoming non-spontaneous at elevated temperatures.
Collectively, the V, Mn, and Zn oxides emerged as optimal candidates as they resisted both the CO-induced reduction and CO2-driven carbonate formation, thereby maintaining structural integrity during the H2S removal.

4.3. Reacting with H2O

Blast furnace gas (BFG) contains significant amounts of saturated water, and the continuous cooling of the gas network leads to the formation of liquid water, which impacts the desulfurization process. Notably, metal oxides may react with H2O in BFG to form hydroxides. As Kariya et al. illustrated, the chemical heat storage systems based on CaO/H2O were expected to utilize waste heat for the purpose of heat storage [74]. Sol-gel based on MgO/H2O, which is known to be a clean, environmentally friendly, inexpensive and readily prepared process, has been used to improve the corrosion resistance of anodized magnesium alloys [75]. Figure 4 illustrates the Gibbs free energy changes for the reaction of each metal oxide with H2O. Due to the high chemical stability of Mn3O4, this oxide exhibits no appreciable reaction with H2O, yielding neither hydroxides nor acids; consequently, Mn3O4 is absent from Figure 4. Analysis of Figure 4 reveals that the ΔG for the reaction of ZnO with H2O remained positive across 100~1000 °C, indicating that the spontaneous formation of Zn(OH)2 did not occur. Conversely, for V2O5, the ΔG values for both reactions—formation of vanadium hydroxide (V(OH)3) and vanadic acid (H3VO4)—remained positive within the same temperature range, demonstrating that V2O5 does not interact with water under these conditions. Therefore, it can be concluded that H2O in BFG has negligible influence on the removal of H2S by V-, Mn-, and Zn-based oxides, and thus the active components were not excluded from consideration.

4.4. Reacting with CH4

Blast furnace gas contains trace amounts of CH4, necessitating evaluation of its potential impact on metal oxides. CH4 may initiate reduction reactions with V, Mn, and Zn oxides, potentially compromising desulfurization performance [76]. Alalwan et al. [77] focused on the CH4 activation reaction on the surface of metal oxide nanoparticles. Through in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and other characterization methods, the reaction pathways and mechanisms of CH4 on the surfaces of CoO, CuO, and α-Fe2O3 are revealed, providing key insights for processes such as chemical looping combustion (CLC) and methane carbon dioxide reforming. Figure 5a demonstrates that Mn3O4 and ZnO maintained positive ΔG values for the CH4 interactions across 100~1000 °C, indicating thermodynamic stability. Conversely, V2O5 undergoes sequential reduction to VO2 and V2O3, though the final step to VO remains non-spontaneous. These findings confirm VO2 and V2O3 as the primary reduction products. Notably, Figure 5b reveals that only V2O5 exhibits spontaneous H2S reactivity within the 100~1000 °C range, while its reduction products (VO2 and V2O3) remain inert. This highlights the deleterious effect of CH4-induced V2O5 reduction, which not only generates inactive phases, but also produces CO2 as a byproduct. Given the irreversible deactivation of V2O5 by CH4, it is excluded from active component selection. In contrast, Mn and Zn oxides demonstrate chemical inertness toward CH4, establishing their superiority over vanadium-based materials.

4.5. Comparison of the Zinc-Manganese-Based Oxides

Following thermodynamic screening based on blast furnace gas composition, the Mn and Zn oxides were identified as optimal active components. Further analysis of their valence-state oxides revealed significant differences. While ZnO remained thermodynamically stable, other zinc oxides (e.g., ZnO2 and Zn2O) exhibited instability. Mn’s 3d54s2 valence electron configuration endows its oxides with half-filled d orbitals across multiple oxidation states, thereby facilitating electron transfer and redox processes [78]. Conversely, Mn oxides demonstrate stronger oxidative capacity and diverse valency (MnO, Mn3O4, Mn2O3, and MnO2) compared to monovalent ZnO. Figure 6 illustrates the ΔG profiles for desulfurization reactions involving Zn and Mn oxides, encompassing the following pathways:
MnO + H2S(g) = MnS + H2O(g),
Mn3O4 + 4H2S(g) = 3MnS + 4H2O(g) + S,
Mn2O3 + 3H2S(g) = 2MnS + 3H2O(g) + S,
MnO2 + 2H2S(g) = MnS + 2H2O(g) + S,
ZnO + H2S(g) = ZnS + H2O(g),
5S + Mn3O4 = 3MnS + 2SO2(g).
Figure 6 reveals that all of the evaluated reactions Equations (4)–(8) exhibited negative ΔG values across 100~1000 °C, confirming spontaneous H2S removal by ZnO and the four Mn oxides. Notably, lower ΔG values indicate stronger sulfur-fixation capacity. These reactions are ranked by spontaneity: Mn3O4 > Mn2O3 > MnO2 > ZnO > MnO. Thermodynamic analysis indicates higher-oxidation-state Mn oxides demonstrate significantly greater H2S reactivity, with stronger oxidation capacity and higher sulfur-fixation potential, compared to ZnO and MnO [79].
Figure 7 presents the results of an equilibrium component analysis for the reactions between ZnO, MnO, Mn3O4, Mn2O3, and MnO2 with H2S at temperatures ranging from 100~1000 °C. To mimic real-world desulfurization processes more accurately, an excess of H2S was employed, with the amount of H2S in the reactants set at 3 kmol (3% concentration). Based on Equations (4)–(8), the quantities of each oxide were determined to ensure that all oxides could remove an equal amount (1.5 kmol) of H2S under H2S-excess conditions: 1.5 kmol of ZnO, 1.5 kmol of MnO, 0.375 kmol of Mn3O4, 0.5 kmol of Mn2O3, and 0.75 kmol of MnO2. It was demonstrated that higher-valence Mn atoms can transfer more electrons, enabling them to remove more H2S and thus possess a larger sulfur capacity, with Mn3O4 exhibiting the greatest sulfur capacity among them.
Notably, the data from Figure 7a,b indicate that temperature had no significant impact on the reactions of ZnO and MnO with H2S, as ZnS, MnS, and H2O were consistently produced across the 100~1000 °C range. Conversely, as shown in Figure 7c, the sulfur-containing products of the reaction between Mn3O4 and H2S included MnS, S, and SO2. From 100~300 °C, reaction Equation (5) dominated, yielding 1.125 kmol of MnS, 0.375 kmol of S, and 1.5 kmol of H2O. As the temperature rose from 300 °C to 400 °C, the amount of S in the products decreased gradually, while that of SO2 increased, and the amount of H2S removed by Mn3O4 also declined. By examining the ΔG change in reaction Equation (9), as shown in Figure 6 (the yellow line in Figure 6), it can be elucidated that the S generated from the reaction between Mn3O4 and H2S could be further oxidized to SO2, where S and H2S are in a competitive relationship as reducing agents. With increasing temperature, the ΔG of Equation (9) drops significantly. Moreover, S volatilizes at higher temperatures, and its reactivity is greatly enhanced, making it more prone to oxidation to SO2. Therefore, above 400 °C, elemental S is absent from the products, and the consumption of Mn3O4 by S leads to a reduction in the amount of H2S removed by Mn3O4.
The product types and change trends shown in Figure 7d,e are generally similar to those in Figure 7c. In the low-temperature range (100~300 °C), reactions Equations (6) and (7) dominated, and both were able to generate an amount of elemental S equal to their own consumption. Therefore, when using high-valence Mn oxides for H2S removal, the temperature should not exceed 300 °C. At this temperature, elemental S can be stably produced, which can be reused as a chemical raw material, presenting significant economic value [80,81]. Additionally, high-valence Mn oxides remove a larger amount of H2S below 300 °C. It should be noted that MnO2 is unstable at high temperatures, undergoing thermal decomposition above 600 °C and being reducible by CO [82,83]. If MnO2 is employed for H2S removal from blast furnace gas, reaction conditions should be carefully controlled to minimize its thermal decomposition and reaction with CO.
In conclusion, high-valence Mn oxides possess advantages such as stronger oxidizing ability, larger sulfur capacity, and the production of elemental S with high re-utilization value. Therefore, the Mn oxides, with Mn3O4 exhibiting the highest sulfur-fixation potential and the largest sulfur capacity, were ultimately selected as the optimal desulfurizers.
The performance of different desulfurizers was compared, as shown in Table 3. Notably, the zinc-based sorbent exhibited high desulfurization efficiency but came with a high cost. Its desulfurization and regeneration processes require high temperature, and it exhibits inferior performance at low temperatures, thereby restricting its application in certain scenarios [26,36,60,84]. Conversely, iron oxide demonstrates low cost but moderate reactivity [85] as its performance is often constrained by poor structural stability and insufficient active sites [16,86,87,88].
Activated carbon relies on its high specific surface area and well-developed pore structure to achieve superior adsorption capacity [89]; however, its poor sulfur capacity and short breakthrough time remains suboptimal [27], necessitating metal impregnation or surface modification to enhance performance [9,90]. Critically, its regeneration process involves high temperatures and induces structural damage, thereby significantly increasing operational costs. By contrast, manganese oxide demonstrated the optimal balance of desulfurization efficiency, sulfur capacity, regenerative performance, and long-term economic viability [61,64,79], rendering it a suitable candidate for BFG desulfurization.
Furthermore, the Mn oxides outperformed other advanced materials like MOFs or perovskites in sulfur capture. Firstly, the H2S removal by the Mn oxides predominantly involved chemical adsorption and oxidation reactions, which are characterized by low activation energy [61]; consequently, the reaction kinetics were notably faster than those of MOFs (which rely on physical adsorption). Secondly, Mn oxides benefit from abundant raw materials (e.g., pyrolusite and battery waste) and straightforward preparation protocols [91], whereas MOFs and perovskites necessitate precious metals or intricate synthetic procedures (coupled with high regeneration energy demands) [92]. Thirdly, Mn oxides exhibit structural stability across 200–600 °C [71]; conversely, MOFs frameworks undergo collapse at > 300 °C. Notably, Mn oxides demonstrate robust tolerance toward common BFG impurities (e.g., CO and CO2), while perovskites, such as LaCoO3, are prone to sulfur poisoning and deactivation in sulfidic atmospheres. Thus, Mn oxides outweigh other materials in industrial sulfur capture applications owing to their rapid reaction kinetics, cost-effectiveness, and superior interference resistance.
In dry desulfurization systems, the surface area and porosity of desulfurizers also play a decisive role in determining H2S removal efficiency and adsorption capacity. Specifically, a larger specific surface area facilitates the provision of additional active sites, thereby accelerating chemical interactions between H2S and metal oxides; additionally, highly porous architectures promote gas diffusion into desulfurizer interiors, enhancing sulfur capacity and extending breakthrough duration. Thus, microstructural tuning via the design of novel desulfurizers represents a crucial strategy for performance enhancement [1,37].

5. Control of Reaction Products in the Regeneration Process of Desulfurizers

Manganese-based desulfurizers generate MnS during H2S removal, which can be regenerated via oxidation with O2. To evaluate the potential chemical reactions between MnS and O2 in the regenerator, HSC Chemistry 6.0 was employed to determine the reaction feasibility and to perform equilibrium composition analysis. Specifically, the reactions and equilibrium products were analyzed across a temperature range of 200~1200 °C at standard atmospheric pressure.
Calculations of the Gibbs free energy changes using HSC Chemistry 6.0 revealed the following primary reactions during MnS regeneration:
MnS + 2O2(g) = MnSO4,
MnS + 1.5O2(g) = MnO + SO2(g),
2MnO + 2SO2(g) + O2(g) = 2MnSO4,
MnS + 3MnSO4 = 4MnO + 4SO2(g),
MnS + O2(g) = Mn + SO2(g),
2Mn + O2(g) = 2MnO,
2MnS + O2(g) = 2MnO + 2S,
S + O2(g) = SO2(g),
2SO2(g) + O2(g) = 2SO3(g),
SO3(g) + MnO = MnSO4,
2S = S2(g),
6MnO + O2(g) = 2Mn3O4,
4MnO + O2(g) = 2Mn2O3,
2MnO + O2(g) = 2MnO2,
4Mn3O4 + O2(g) = 6Mn2O3,
Mn3O4 + O2(g) = 3MnO2,
2Mn2O3 + O2(g) = 4MnO2,
3MnS + 5O2(g) = Mn3O4 + 3SO2(g),
2MnS + 3.5O2(g) = Mn2O3 + 2SO2(g),
MnS + 2O2(g) = MnO2 + SO2(g),
Mn3O4 + 3SO2(g) + O2(g) = 3MnSO4,
2Mn2O3 + 4SO2(g) + O2(g) = 4MnSO4,
MnO2 + SO2(g) = MnSO4,
MnS + 5MnSO4 = 2Mn3O4 + 6SO2(g),
MnS + 7MnSO4 = 4Mn2O3 + 8SO2(g).
Reactions Equations (21)–(26) involved the further oxidation of MnO to higher-oxidation-state oxides, which gave rise to the subsequent Reactions Equations (27)–(34). When considering MnO alone, Figure 8a illustrates the ΔsG profiles for the MnS regeneration reactions. Figure 8b presents the ΔG changes for the MnO oxidation pathways. Thermodynamic analysis confirmed the thermal instability of MnO2 as Reactions Equations (25) and (26) exhibited a sign change in ΔG near 600 °C, indicating MnO2 decomposition at this temperature threshold.
The regeneration of MnS is influenced by temperature variations, O2 stoichiometry, and concentration. Reaction Equation (11) specified that the complete oxidation of 1 kmol MnS to MnO and SO2 necessitates 1.5 kmol O2. Using MnO formation as a model, reactions during regeneration were analyzed, as shown in Figure 9a,b, revealing that the products were governed by reactions Equations (10)–(13).
Notably, Equations (10) and (11) exhibited robust negative ΔG across 200~1200 °C with minimal temperature dependence, whereas Equations (12) and (13) demonstrated pronounced temperature sensitivity. Equation (13)’s ΔG decreased sharply with temperature elevation, transitioning to negative near 600 °C, which indicates MnSO4 undergoes spontaneous decomposition with MnS to form MnO and SO2 at ≥600 °C.
Equation (12) maintained negative ΔG between 200~1000 °C but increased with temperature, reflecting stronger reactivity at lower temperatures. Since Equations (11) and (12) represented sub-reactions of Equation (10), the MnO and SO2 generated by Equation (11) at 200 °C further reacted via Equation (12) to form MnSO4. Consequently, Equation (10) dominated at low temperatures, yielding 0.75 kmol of MnSO4 and 0.25 kmol of unreacted MnS. As the temperature increased, Equation (12)’s ΔG elevation reduced MnSO4 and unreacted MnS while increasing MnO and SO2. When the temperature reached 600 °C, MnSO4 reacted with MnS to decompose into MnO and SO2. It can be seen that Equations (10) and (13) are components of Equation (11); as such, at high temperatures, the reaction was mainly dominated by Equation (11), and the products were MnO and SO2.
During MnS oxidation regeneration, reactions Equations (14), (16), and (18) generated metallic Mn, elemental S, and SO3 gas, respectively. These products were rapidly converted: Mn and S oxidized to MnO and SO2, while SO3 reacted with MnO to form MnSO4. Specifically, Equations (14)–(17) represented sub-reaction pathways for Equation (11), and Equations (18) and (19) served as sub-reactions for Equation (13). Given the thermodynamic favorability of Equations (15), (17) and (19), Mn, S, and SO3 acted as transient intermediates and, thus, do not appear in Figure 9b. Reaction Equation (20) was restricted to high-temperature, oxygen-deficient environments. Notably, S preferentially reacted with O2 over forming S2 gas, resulting in trace S2 gas formation at elevated temperatures only. Figure 9a illustrates partial S2 gas generation at high temperatures due to O2 limitation.
Under O2-sufficient conditions, MnO undergoes further oxidation. Reactions Equations (21)–(26) describe the progression of Mn oxides to higher oxidation states, initiating secondary reactions Equations (27)–(34). Figure 9b shows Mn3O4 formation above 400 °C, indicating partial MnO oxidation. The limited extent of MnO oxidation likely stems from the 1.5 kmol O2 dosage (matching Equation (11) stoichiometry for 1 kmol of MnS oxidation), which may be insufficient to drive complete oxidation to higher valence states.
The molar ratio of reactants specified in Equation (27) was adopted to elevate the O2 dosage to 1.67 kmol for component analysis simulation, as presented in Figure 9c. The observed phenomenon clearly demonstrates that the MnO content decreased rapidly with increasing temperature, while Mn3O4 and Mn2O3 concentrations increased. This trend elucidates that augmented O2 supply promotes further oxidation of MnO to higher-valence manganese oxides. Notably, MnO2 absence in products can be attributed to its thermal decomposition at elevated temperatures. The accelerated MnO consumption at higher temperatures is primarily ascribed to enhanced oxidation kinetics and oxygen reactivity, which are both temperature-dependent. Conversely, when temperature exceeds 900 °C, MnO reaccumulates with concomitant O2 evolution, presumably due to the thermodynamic inhibition of exothermic MnO oxidation under such conditions.
Following the stoichiometric ratios defined in Equations (10), (28), and (29), O2 dosages were further increased to 1.75 kmol and 2 kmol, yielding results shown in Figure 9d,e. Figure 9d exhibits similar trends to Figure 9c, but with systematically reduced MnO content and earlier O2 evolution. Significantly, Figure 9e demonstrates that, under O2-sufficient conditions, the Mn3O4 and Mn2O3 concentrations and their growth rates surpassed those of MnO, albeit they were accompanied by minor SO3 formation. This indicates that excess O2 not only facilitates MnO oxidation, but also promotes SO2 oxidation.
Although elevated O2 levels enhance MnO oxidation, the following critical consideration arise: increasing O2 dosage delays MnSO4 elimination until temperatures exceed 900 °C. Since MnSO4 is an undesirable byproduct in the regeneration process, such high-temperature conditions pose risks of manganese oxide sintering and equipment degradation. Conversely, insufficient O2 supply (e.g., 1 kmol of O2) leads to incomplete oxidation, as shown by the MnS presence in Figure 9a, which violates regeneration requirements.
Collectively, these results posit that 1.5 kmol of O2 per kmol of MnS represents the optimal dosage for regeneration. This configuration yields substantial MnO and SO2 production while avoiding excessive temperature elevation and associated sintering risks. Both O2 deficiency and excess introduce undesirable outcomes: incomplete oxidation versus operational challenges.
The optimal oxygen dosage for MnS oxidative regeneration was determined to be 1.5 kmol. Subsequent equilibrium composition analysis of the regeneration process under varying oxygen concentrations, as depicted in Figure 10, reveals that the reaction products exhibited consistent species, and the curve variations were largely comparable. This observation demonstrates that lower oxygen concentrations slightly reduced the temperature thresholds for MnS and MnSO4 disappearance, which is consistent with previous studies [93,94,95]. The MnS-O2 reaction is highly exothermic with elevated reactivity; excessively high oxygen concentrations may trigger violent reactions leading to localized overheating, thereby increasing risks of desulfurizer sintering and equipment damage [96,97]. Therefore, oxygen dilution mitigates MnO sintering and extends operational lifespan.
Collectively, providing 1.5-fold stoichiometric oxygen achieves complete MnS oxidation at reduced temperatures. Oxygen concentration dilution further lowers regeneration temperatures while preventing thermal runaway-induced sintering and equipment degradation. At 1.5-fold stoichiometry with 5% O2, full MnS conversion was achieved at 700 °C, yielding MnO, SO2, and minor Mn3O4. This characteristic is highly compatible with the characteristics of industrial off-gas. For example, the flue gas of steel plants (usually containing 5~15% O2), or the low-oxygen gas in the tail gas of chemical plants, can be directly used as the regeneration gas source, avoiding the additional energy consumption of pure oxygen preparation or high-concentration oxygen dilution. Compared with the traditional method of using high-purity oxygen, the use of industrial waste gas as the regeneration gas source can significantly reduce the operating cost.
For industrial implementation, the SO2-rich tail gas can be directly channeled into a sulfuric acid production unit. The contact process typically achieves > 99% SO2 conversion efficiency, generating commercial-grade sulfuric acid that can be reused in steel pickling, water treatment, or sold as a byproduct to offset desulfurization costs. For example, each ton of SO2 processed yields approximately 1.5 tons of sulfuric acid, creating an economic benefit of ~USD 200–300 per ton of MnS regenerated, while simultaneously ensuring SO2 emissions comply with China’s Iron and Steel Industry Air Pollutant Emission Standards.

6. Conclusions

This study systematically employed thermodynamic analysis to screen suitable metallic desulfurizers and to investigate the reaction product regulation during desulfurizer regeneration. Key findings are presented as follows:
(1)
Thermodynamic evaluations of reactions between blast furnace gas components and candidate metal oxides identified manganese oxides as the most promising H2S sorbent. These materials exhibit advantages, including non-radioactive characteristics; cost-effectiveness; high sulfur retention capacity; chemical inertness toward CO2, CO, and CH4; and unique stability across multiple high-valence Mn oxide phases.
(2)
Comprehensive characterization of four manganese oxide phases revealed sulfur retention capacities in the following descending order: Mn3O4 > Mn2O3 > MnO2 > MnO. High-valence Mn oxides demonstrated superior oxidation potential, larger sulfur storage capacities, and the ability to generate elemental sulfur with high industrial utility. Notably, MnO2 underwent thermal decomposition at elevated temperatures and reacted with CO, necessitating stringent control of the reaction parameters to suppress undesirable side reactions.
(3)
Compositional analysis of MnS oxidation indicated that 1.5 kmol of O2 per kmol of MnS represents the optimal stoichiometry for producing MnO and SO2. Oxygen deficiency resulted in incomplete regeneration, whereas excess oxygen induced significant temperature excursions, leading to manganese oxide sintering and accelerated equipment degradation. Oxygen concentration dilution effectively mitigated thermal runaway while reducing regeneration temperatures. Under 1.5-fold stoichiometric conditions with 5% O2, complete MnS conversion was achieved above 700 °C, yielding MnO, SO2, and trace amounts of Mn3O4.
(4)
The present study primarily relied on thermodynamic equilibrium calculations, which do not account for kinetic factors (e.g., reaction rates and mass transfer limitations) that may influence practical H2S removal and regeneration processes. In our future work, experimental validation will be carried out to bridge the gap between thermodynamic predictions and practical applications, ensuring the reliability of Mn oxide-based desulfurizers in real blast furnace gas treatment systems.

Author Contributions

Conceptualization, Y.X. and H.G.; methodology, Y.X. and S.P.; software, Y.X.; validation, H.G.; formal analysis, H.T.; investigation, Z.H.; data curation, Y.Y.; writing—original draft preparation, Y.X.; writing—review and editing, H.G. and H.T.; supervision, H.G. and H.T.; project administration, Y.X.; funding acquisition, H.T. and Y.X. All authors have read and agreed to the published version of the manuscript.

Funding

This work was supported by the National Natural Science Foundation of China (No. 52104391 Y.X., 52476176 H.T.) and the Natural Science Foundation of Hunan Province, China (No. 2022JJ40501 Y.X., 2024JJ5032 Z.H.).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The original contributions presented in this study are included in the article. Further inquiries can be directed to the corresponding authors.

Acknowledgments

The authors wish to acknowledge Changsha University of Science and Technology for the provision of computer stations.

Conflicts of Interest

The authors declare no conflicts of interest.

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Materials 18 02918 g001
Figure 1. Flow chart of the H2S removal and regeneration process by metal oxides (M represents metal elements).
Figure 1. Flow chart of the H2S removal and regeneration process by metal oxides (M represents metal elements).
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Figure 2. The fixing-sulfur potentiality of the 22 types of metal oxides when subjected to temperatures from 100 °C to 1000 °C: (a) The reaction of Equation (2). (b) The reaction of Equation (3).
Figure 2. The fixing-sulfur potentiality of the 22 types of metal oxides when subjected to temperatures from 100 °C to 1000 °C: (a) The reaction of Equation (2). (b) The reaction of Equation (3).
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Materials 18 02918 g003
Figure 3. The ∆G variation of the 14 types of metal oxides under different temperatures: (a) The chemical reaction of the metal oxides with CO. (b) The chemical reaction of the metal oxides with CO2.
Figure 3. The ∆G variation of the 14 types of metal oxides under different temperatures: (a) The chemical reaction of the metal oxides with CO. (b) The chemical reaction of the metal oxides with CO2.
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Materials 18 02918 g004
Figure 4. The changes in the ΔG of the Zn and V oxides at different temperatures (when reacting with H2O).
Figure 4. The changes in the ΔG of the Zn and V oxides at different temperatures (when reacting with H2O).
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Figure 5. (a) The changes in the ΔG of the Zn, Mn, and V oxides at different temperatures (when reacting with CH4). (b) The changes in the ΔG of the V2O5, VO2, and V2O3 at different temperatures (when reacting with H2S).
Figure 5. (a) The changes in the ΔG of the Zn, Mn, and V oxides at different temperatures (when reacting with CH4). (b) The changes in the ΔG of the V2O5, VO2, and V2O3 at different temperatures (when reacting with H2S).
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Figure 6. The ΔG changes in the desulfurization of the Zn and Mn oxides at different temperatures.
Figure 6. The ΔG changes in the desulfurization of the Zn and Mn oxides at different temperatures.
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Materials 18 02918 g007aMaterials 18 02918 g007b
Figure 7. The production of various substances during the H2S removal process of Zn and Mn oxides: (a) 1.5 kmol of ZnO, (b) 1.5 kmol of MnO, (c) 0.375 kmol of Mn3O4, (d) 0.5 kmol of Mn2O3, and (e) 0.75 kmol of MnO2.
Figure 7. The production of various substances during the H2S removal process of Zn and Mn oxides: (a) 1.5 kmol of ZnO, (b) 1.5 kmol of MnO, (c) 0.375 kmol of Mn3O4, (d) 0.5 kmol of Mn2O3, and (e) 0.75 kmol of MnO2.
Materials 18 02918 g007aMaterials 18 02918 g007b
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Figure 8. The changes in the ΔG of the various reactions during the following MnS regeneration processes: (a) involving MnO only, and (b) when MnO continued to be oxidized into high valence oxides.
Figure 8. The changes in the ΔG of the various reactions during the following MnS regeneration processes: (a) involving MnO only, and (b) when MnO continued to be oxidized into high valence oxides.
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Figure 9. The production of various substances during the regeneration process of 1 kmol of MnS: (a) 1 kmol concentration of 5% oxygen, (b) 1.5 kmol concentration of 5% oxygen, (c) 1.67 kmol concentration of 5% oxygen, (d) 1.75 kmol concentration of 5% oxygen, and (e) 2 kmol concentration of 5% oxygen.
Figure 9. The production of various substances during the regeneration process of 1 kmol of MnS: (a) 1 kmol concentration of 5% oxygen, (b) 1.5 kmol concentration of 5% oxygen, (c) 1.67 kmol concentration of 5% oxygen, (d) 1.75 kmol concentration of 5% oxygen, and (e) 2 kmol concentration of 5% oxygen.
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Figure 10. The production of various substances during the regeneration process of 1 kmol of MnS: (a) 1.5 kmol concentration of 20% oxygen, (b) 1.5 kmol concentration of 10% oxygen, (c) 1.5 kmol concentration of 5% oxygen, and (d) 1.5 kmol concentration of 1% oxygen.
Figure 10. The production of various substances during the regeneration process of 1 kmol of MnS: (a) 1.5 kmol concentration of 20% oxygen, (b) 1.5 kmol concentration of 10% oxygen, (c) 1.5 kmol concentration of 5% oxygen, and (d) 1.5 kmol concentration of 1% oxygen.
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Table 1. Sulfur content of the blast furnace gas (mole fraction) unit: μmol/mol.
Table 1. Sulfur content of the blast furnace gas (mole fraction) unit: μmol/mol.
ComponentHydrogen Sulfide (H2S)Carbon Based Sulfur (COS)Methyl
Mercaptan (CH3SH)		Thiophene
(C4H4S)		Other
Content30.773.80.03230.0176<0.01
Table 2. The main studies on the desulfurization performance and cost of metal oxides.
Table 2. The main studies on the desulfurization performance and cost of metal oxides.
Metal OxideDesulfurization Efficiency/%Sulfur Capacity
/(mg/g-Sorbent)		Experimental Temperature/°CH2S Concentration
/vol.%		Desulfurizer Cost
/(Yuan/Kg-Sorbent)		Refs.
Manganese oxide>991421800.312[64]
Vanadium oxide986.051800.388[65]
Copper oxide>9994–13730–800.035150[65]
Iron oxide1001.0–2.5250.02–0.05790[66]
Magnesium oxide9932.7300.06180[27]
Zinc oxide9938.5300.0635[27]
Table 3. Comparative analysis of the performance of the different desulfurizers.
Table 3. Comparative analysis of the performance of the different desulfurizers.
SorbentsEfficiency (%)Capacity (mg/g)ReusabilityComprehensive CostRefs.
Zinc-based >99%48.7NoDifficult to regenerate, hazardous waste[26,36,60,84]
Iron-based >99%16NoHigh replacement[16,85,86,87,88]
Activated carbon ~95%3NoProne to blockage[9,27,89,90]
Manganese-based~99%142YesLong service life[61,64,79]
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Xuan, Y.; Peng, S.; Tian, H.; Hu, Z.; Yin, Y.; Gao, H. Selection of High-Performance Sorbent for H2S Removal and Regulation of Reaction Products via Thermodynamic Simulation. Materials 2025, 18, 2918. https://doi.org/10.3390/ma18122918

AMA Style

Xuan Y, Peng S, Tian H, Hu Z, Yin Y, Gao H. Selection of High-Performance Sorbent for H2S Removal and Regulation of Reaction Products via Thermodynamic Simulation. Materials. 2025; 18(12):2918. https://doi.org/10.3390/ma18122918

Chicago/Turabian Style

Xuan, Yanni, Shuaicheng Peng, Hong Tian, Zhangmao Hu, Yanshan Yin, and Haitao Gao. 2025. "Selection of High-Performance Sorbent for H2S Removal and Regulation of Reaction Products via Thermodynamic Simulation" Materials 18, no. 12: 2918. https://doi.org/10.3390/ma18122918

APA Style

Xuan, Y., Peng, S., Tian, H., Hu, Z., Yin, Y., & Gao, H. (2025). Selection of High-Performance Sorbent for H2S Removal and Regulation of Reaction Products via Thermodynamic Simulation. Materials, 18(12), 2918. https://doi.org/10.3390/ma18122918

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