Low-temperature hydrolysis of carbonyl sulfide in blast furnace gas using Al2O3-based catalysts with high oxidation resistance

Cao, Rui; Ning, Ping; Wang, Xueqian; Wang, Langlang; Ma, Yangmin; Xie, Yibing; Zhang, Hui; Qu, Jiaxin

doi:10.1016/j.fuel.2021.122295

Cited by 50 publications

(11 citation statements)

References 41 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

Section: Resultsmentioning

confidence: 99%

“…The Na-doping sample showed a relatively regular prismatic crystal structure (Figure 8b), while the K-doping sample formed a kind of fine nanorod-like structure (Figure 8c), which can provide more gas contact surfaces for the reaction. 23 According to the element mapping, it was proved that Na and K are uniformly distributed in the respective samples. BET analysis showed that the pore volume of samples prepared by the deposition of Na 2 O and K 2 O decreased.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Contribution of Na/K Doping to the Activity and Mechanism of Low-Temperature COS Hydrolysis over TiO₂-Al₂O₃ Based Catalyst in Blast Furnace Gas

Liu

Shen

et al. 2022

ACS Omega

View full text Add to dashboard Cite

As an organic sulfur pollutant generated in blast furnace gas, carbonyl sulfide (COS) has attracted more attention due to its negative effects on the environment and economy. The TiO 2 -Al 2 O 3 composite metal oxide (Ti 0.5 Al) with uniformly dispersed particles was prepared by the co-precipitation method. And on this basis, a series of Na/K-doped catalysts were prepared separately. The activity evaluation results showed that the introduction of Na/K significantly improved the low-temperature COS hydrolysis activity, which exhibited a COS conversion of 98% and H 2 S yield of 95% at 75 °C with 24,000 h –1 . And K showed a better promoting effect than Na. Brunauer–Emmett–Teller (BET) results revealed the increased mesopore proportion of Na/K-modified catalysts. X-ray diffraction (XRD) and scanning electron microscopy (SEM) showed that Na and K formed prismatic and nanorod-like structures, respectively. More weakly basic sites with enhanced intensity and decreased O ads /O lat content contributed to the excellent catalytic activity, as certified by the results of CO 2 temperature-programmed desorption (CO 2 -TPD) and X-ray photoelectron spectroscopy (XPS). It was also proposed that the decrease of weakly basic sites ultimately deactivated catalyst activity. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) showed that the introduction of Na/K enhanced the dissociation of H 2 O, and the generated abundant hydroxyl groups promoted the adsorption of COS and formed surface transition species, such as HSCO 2 – and HCO 3 – .

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Contribution of Na/K Doping to the Activity and Mechanism of Low-Temperature COS Hydrolysis over TiO₂-Al₂O₃ Based Catalyst in Blast Furnace Gas

Liu

Shen

et al. 2022

ACS Omega

View full text Add to dashboard Cite

show abstract

“…It is well known that COS hydrolysis is a typically base-catalyzed reaction. 53,54 First, COS and H 2 O were coadsorbed on the surface of N-HLCF-xs, then the H 2 O was dissociated to form OH*, and the released H* was captured by pyridine structural base sites (C 6 N−H) in the N-HLCF-xs. 55 After that, the adsorbed and activated COS (COS*) reacts with OH* and generates CO 2 and HS*, 56 which further combines with the adsorbed H* in C 6 NH to form H 2 S (as depicted in Figure 9).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Based on the structural characteristics of N-HLCF-xs catalysts and their excellent activities in COS hydrolysis and H 2 S selective oxidation, a possible mechanism for these desulfurization processes was proposed. It is well known that COS hydrolysis is a typically base-catalyzed reaction. , First, COS and H 2 O were coadsorbed on the surface of N-HLCF-xs, then the H 2 O was dissociated to form OH*, and the released H* was captured by pyridine structural base sites (C 6 N–H) in the N-HLCF-xs . After that, the adsorbed and activated COS (COS*) reacts with OH* and generates CO 2 and HS*, which further combines with the adsorbed H* in C 6 NH to form H 2 S (as depicted in Figure ).…”

Section: Resultsmentioning

confidence: 99%

Efficiently Integrated Desulfurization from Natural Gas over Zn-ZIF-Derived Hierarchical Lamellar Carbon Frameworks

et al. 2022

View full text Add to dashboard Cite

Selective removal of carbonyl sulfide (COS) and hydrogen sulfide (H 2 S) is the key step for natural gas desulfurization due to the highly toxic and corrosive features of these gaseous sulfides, and efficient and stable desulfurizers are urgently needed in the industry. Herein, we report a class of nitrogen-functionalized, hierarchically lamellar carbon frameworks (N-HLCF-xs), which are obtained from the structural transformation of Zn zeolitic imidazolate frameworks via controllable carbonization. The N-HLCF-xs possess the desirable characteristics of large Brunauer−Emmett−Teller surface areas (645−923 m 2 /g), combined primary three-dimensional microporosity and secondary two-dimensional lamellar microstructure, and high density of nitrogen base sites with enhanced pyridine ratio (17.52 wt %, 59.91%). The anchored nitrogen base sites in N-HLCF-xs show improved accessibility, which boosts their interaction with acidic COS and H 2 S. As expected, N-HLCF-xs can be employed as multifunctional and efficient desulfurizers for selective removal of COS and H 2 S from natural gas. COS was first transformed into H 2 S via catalytic hydrolysis, and the produced H 2 S was then captured and separated and catalyzed oxidation into elemental sulfur. The above continuous processes can be achieved with solo N-HLCF-xs, giving extremely high efficiencies and reusability. Their integrated desulfurization performance was better than many desulfurizers used in the area, such as activated carbon, β zeolite, MIL-101(Fe), K 2 CO 3 /γ-Al 2 O 3 , and FeO x /TiO 2 .

show abstract

“…For H 2 S, many removal technologies have been applied by different research groups including adsorption, the Claus process, and selective catalytic oxidation. − The oxidation of H 2 S to produce sulfur at a relatively low concentration is considered one of the most promising strategies to eliminate H 2 S due to its high reactivity, efficient removal ability, and mild reaction conditions. , Different from H 2 S, the elimination of COS is much more difficult owing to its relative chemical inertness. Many approaches have been developed to remove COS from gas, including hydrogenation conversion, oxidation conversion, adsorption, and catalytic hydrolysis. − With respect to the simultaneous removal of H 2 S and COS, the assembly technique such as hydrolysis plus adsorption is adopted in the industry, but COS hydrolysis catalysts can be easily disabled because of H 2 S oxidation, sulfate formation, and poisoning by HCl. In addition, although large sulfur capacity can be achieved over carbon-based materials through adsorption and oxidation of H 2 S, the adsorption of COS over activated carbon is always weak owing to the low polarity of COS. , Therefore, the development of high-efficiency and low-cost materials to remove sulfides from BFG is still a long-term goal in the field.…”

Section: Introductionmentioning

confidence: 99%

Resource Utilization of Spent Activated Coke as an Efficient Material for Simultaneous Removal of COS and H₂S

Liu

et al. 2022

Energy Fuels

View full text Add to dashboard Cite

The desulfurization of blast furnace gas (BFG) is highly desired by iron and steel enterprises to realize its resource utilization with no environmental pollution. In this work, spent activated coke (SAC) modified by NaOH was innovatively reused as an efficient material for the removal of carbonyl sulfide (COS) and sulfuretted hydrogen (H 2 S) from BFG with admirable breakthrough sulfur capacities of 126.58 and 141.62 mg/g, respectively, and 100% removal efficiency of both COS and H 2 S could be reached with the total sulfur capacity of COS and H 2 S as high as 116.60 mg/g in the purification of the simulative BFG gas. The removal behaviors manifested that the removal process included catalytic hydrolysis of COS to H 2 S and subsequent oxidation of H 2 S to immobilize these sulfur species in the form of S 8 . The multiple structural characterizations (X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), H 2 -temperature-programmed reduction (TPR)) further revealed that the surface carbonyl and pyridine/pyrrolic groups together with the loaded hydroxyl ion enhanced the COS hydrolysis and the subsequent oxidation of H 2 S. The modified SAC possessed much richer pore structures and active groups than either fresh activated coke (FAC) or high specific surface area activated carbon (HAC). At the same time, a recycling scheme suitable for SAC after removing H 2 S and COS was proposed. The demonstrated excellent simultaneous removal capacity of COS and H 2 S over the modified SAC will provide a promising technical route for desulfurization of BFG with high efficiency and low cost.

show abstract

Low-temperature hydrolysis of carbonyl sulfide in blast furnace gas using Al2O3-based catalysts with high oxidation resistance

Cited by 50 publications

References 41 publications

Contribution of Na/K Doping to the Activity and Mechanism of Low-Temperature COS Hydrolysis over TiO₂-Al₂O₃ Based Catalyst in Blast Furnace Gas

Contribution of Na/K Doping to the Activity and Mechanism of Low-Temperature COS Hydrolysis over TiO₂-Al₂O₃ Based Catalyst in Blast Furnace Gas

Efficiently Integrated Desulfurization from Natural Gas over Zn-ZIF-Derived Hierarchical Lamellar Carbon Frameworks

Resource Utilization of Spent Activated Coke as an Efficient Material for Simultaneous Removal of COS and H₂S

Contact Info

Product

Resources

About

Low-temperature hydrolysis of carbonyl sulfide in blast furnace gas using Al2O3-based catalysts with high oxidation resistance

Cited by 50 publications

References 41 publications

Contribution of Na/K Doping to the Activity and Mechanism of Low-Temperature COS Hydrolysis over TiO2-Al2O3 Based Catalyst in Blast Furnace Gas

Contribution of Na/K Doping to the Activity and Mechanism of Low-Temperature COS Hydrolysis over TiO2-Al2O3 Based Catalyst in Blast Furnace Gas

Efficiently Integrated Desulfurization from Natural Gas over Zn-ZIF-Derived Hierarchical Lamellar Carbon Frameworks

Resource Utilization of Spent Activated Coke as an Efficient Material for Simultaneous Removal of COS and H2S

Contact Info

Product

Resources

About

Contribution of Na/K Doping to the Activity and Mechanism of Low-Temperature COS Hydrolysis over TiO₂-Al₂O₃ Based Catalyst in Blast Furnace Gas

Contribution of Na/K Doping to the Activity and Mechanism of Low-Temperature COS Hydrolysis over TiO₂-Al₂O₃ Based Catalyst in Blast Furnace Gas

Resource Utilization of Spent Activated Coke as an Efficient Material for Simultaneous Removal of COS and H₂S