Regeneration of sulfur-poisoned Cu-SSZ-13 catalysts: Copper speciation and catalytic performance evaluation

Mesilov, V. V.; Dahlin, Sandra; Bergman, Susanna L.; Xi, Shibo; Han, Joonsoo; Olsson, Louise; Pettersson, Lars J.; Bernasek, S. L.

doi:10.1016/j.apcatb.2021.120626

Cited by 25 publications

(21 citation statements)

References 48 publications

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“…The XANES of PC5 shows a higher intensity of the white line and a shift of the white line maximum to lower energies as compared to that seen for PC4 (Figure ). The differences in white line shape of PC4 and PC5 can indicate variations in charge transfer processes between Cu ions and their surrounding ligands. , An increased intensity of the postedge feature at around 9015 eV is also observed (inset of Figure ). Nevertheless, PC5 does not exhibit the rising-edge shoulder, which is observed for PC4.…”

Section: Resultsmentioning

confidence: 95%

“…Abundant studies on sulfur poisoning of Cu-SSZ-13 have been performed. − The sulfur poisoning led to decreased deNO x activity at temperatures below 350 °C . This deactivation was mainly associated with the poisoning of active Cu sites .…”

Section: Introductionmentioning

confidence: 99%

“…Although Cu-SSZ-13 catalysts have been widely investigated using Cu K-edge X-ray absorption spectroscopy (XAS), − there are only a few XAS studies concerning sulfur-poisoned catalysts. − Shih et al found a higher fraction of nonreduced Cu II for poisoned catalysts in NO/NH 3 as compared to fresh catalysts. In addition to a suppressed reduction of Cu ions, we also found decreased mobility of Cu ions in the S-poisoned catalyst .…”

Section: Introductionmentioning

confidence: 99%

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Impact of Biodiesel-Based Phosphorus and Sulfur on Copper Speciation of Cu-SSZ-13 Catalysts: XAFS Scanning during H₂-TPR

et al. 2022

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Biodiesel is a promising renewable fuel, which may help to limit our dependence on fossil fuels. However, the presence of contaminants in biodiesel can affect the Cu speciation of the Cu-SSZ-13 selective catalytic reduction (SCR) catalyst, resulting in its deactivation and decreased durability. In situ Cu K-edge X-ray absorption fine structure (XAFS) scanning during a temperature-programmed reduction in hydrogen (H2-TPR) has been applied here for the analysis of Cu speciation in Cu-SSZ-13 catalysts aged using pure and contaminated biodiesel fuels. XAFS data were analyzed using the multivariate curve resolution alternating least-squares (MCR-ALS) method. While only reduction from CuII to CuI was observed at temperatures below 500 °C for the catalyst aged using pure biodiesel, a one-step reduction of CuII to Cu0 at temperatures between 400 and 500 °C was found for the catalyst aged using P-doped biodiesel. The transformation of isolated CuII species to CuII clusters was suggested for the catalyst as a result of aging using P-doped biodiesel. The catalyst aged using S-doped biodiesel showed mainly the reduction of isolated CuII to CuI, which was inhibited as compared to that observed for the catalyst aged using pure biodiesel. The reduction of the catalyst aged using P+S-doped biodiesel led to the reduction of CuII to both CuI and Cu0. The phosphorus was responsible for the formation of CuII clusters during aging of the catalyst using P+S-doped biodiesel. This study reveals that the presence of phosphorus in biofuels should be strictly regulated to avoid major changes in the Cu speciation of Cu-SSZ-13 catalysts.

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Section: Resultsmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Impact of Biodiesel-Based Phosphorus and Sulfur on Copper Speciation of Cu-SSZ-13 Catalysts: XAFS Scanning during H₂-TPR

et al. 2022

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“…However, CuSO 4 only decomposed at higher temperatures (>550 °C), indicating that irreversible poisoning occurred. 24,25 Decreasing the poisoning of copper active sites is a hot research topic on Cu-SSZ-13 catalysts. There are mainly five strategies for improving the SO 2 resistance of NH 3 -SCR catalysts.…”

Section: Introductionmentioning

confidence: 99%

Promotion Effect of Fe Species on SO₂ Resistance of Cu-SSZ-13 Catalysts for NO_x Reduction by NH₃

Xie

Liu

Ruan

2022

Ind. Eng. Chem. Res.

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In this study, homogeneous precipitation and self-assembly methods were used for the preparation of two kinds of Fe-containing Cu-SSZ-13 catalysts (CuFe-SSZ-13 HDP and Cu-SSZ-13@Fe x O y ), respectively. Both of them maintained a NO x conversion of ∼46% at 225 °C after poisoning with 100 ppm SO 2 at 400 000 h −1 . Fe species promoted the SO 2 resistance of Cu-SSZ-13 significantly. The structure−activity relationship and reaction mechanism were explored to explain the promotion effect in detail. For CuFe-SSZ-13 HDP , some active Fe species were maintained during SO 2 poisoning, which increased the reactivity between NH 3 -adsorbed species and NO x in the presence of SO 2 . The characteristic contributed to its better SO 2 tolerance. For Cu-SSZ-13@Fe x O y , Fe species protected some Cu species from forming CuSO 4 and decreased the amount of ammonium sulfate on the catalyst surface due to their special distribution. Better NO x activation after SO 2 poisoning was the most important reason for its better SO 2 tolerance.

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“…Therefore, various methods have been developed to abate NOx emission from stationary sources. Among them, selective catalytic reduction of NOx by NH3 (NH3-SCR) is the most effective technology to abate NOx and has been successfully applied in coal-fired power plants 3,4 . The catalyst is the key in NH3-SCR method.…”

Section: Introductionmentioning

confidence: 99%

Effect of Potassium on the Performance of a CuSO4/TiO2 Catalyst Used in the Selective Catalytic Reduction of NOx by NH3

Yu¹,

Geng²,

Wei³

et al. 2022

Acta Physico Chimica Sinica

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Owing to its renewability, abundance, and low environmental impact, biomass is considered to be a viable eco-friendly fuel. Various biofuelfired power plants have been built worldwide to reduce carbon emissions. Potassium (K) is a typical impurity in the flue gas from biofuel combustion that can deactivate the catalyst used in the selective catalytic reduction of NOx by ammonia (NH3-SCR). CuSO4/TiO2, with excellent sulfur dioxide tolerance, is thought to be a promising vanadium-free catalyst for NH3-SCR; however, the influence of K on the CuSO4/TiO2 catalyst is still unknown. Therefore, in this study, the effect of K on the NH3-SCR performance of CuSO4/TiO2 were investigated and compared with the effect on the performance of the commercial V2O5-WO3/TiO2 (VWTi) catalyst. K-poisoned catalysts were prepared via wet impregnation using potassium acetate as the K source. Nitrogen (N2) adsorption-desorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), NH3-temperature programmed desorption (NH3-TPD), H2temperature programmed reduction (H2-TPR), and in situ diffuse reflectance infrared Fourier-transform spectroscopy (in situ DRIFTS) were used to characterize the prepared catalysts. The NOx conversion over CuSO4/TiO2 with 1.0% (w) K was 92.1% (at 350 °C), which was higher than the conversion (75.1%) achieved over the commercial VWTi catalyst with the same K content. The XRD, XPS, and H2-TPR results suggested that K reacted with the CuSO4 in the CuSO4/TiO2 catalyst to form CuO and K2SO4. The presence of CuO enhanced the oxidation of NH3 to N2O, NO, and NO2 during NH3-SCR, thereby decreasing the NOx conversion and N2 selectivity over CuSO4/TiO2. Moreover, based on the results from NH3-TPD and in situ DRIFTS of NH3 adsorption, it can be concluded that the Brønsted acid sites (S-OH) were poisoned by K, which restrained the adsorption of NH3 on CuSO4/TiO2. Additionally, the high K content altered the pore structure of the catalyst, leading to a decrease in the specific surface area. However, according to the in situ DRIFTS results, NH3-SCR over K-poisoned CuSO4/TiO2 still followed the Eley-Rideal mechanism: First, NH3 was adsorbed on the Lewis and Brønsted acid sites of the catalyst, and then gaseous NO and O2 reacted with the adsorbed NH3/NH4+ on the acid sites, resulting in the formation of N2 and H2O. Notably, the abundance of acid sites and surface-adsorbed oxygen species on CuSO4/TiO2 could be the main reason for its higher resistance to K-poisoning. In conclusion, our current findings suggested that CuSO4/TiO2 might be a suitable NH3-SCR catalyst for use in the flue gas streams from biofuel-fired power plants.

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Regeneration of sulfur-poisoned Cu-SSZ-13 catalysts: Copper speciation and catalytic performance evaluation

Cited by 25 publications

References 48 publications

Impact of Biodiesel-Based Phosphorus and Sulfur on Copper Speciation of Cu-SSZ-13 Catalysts: XAFS Scanning during H₂-TPR

Impact of Biodiesel-Based Phosphorus and Sulfur on Copper Speciation of Cu-SSZ-13 Catalysts: XAFS Scanning during H₂-TPR

Promotion Effect of Fe Species on SO₂ Resistance of Cu-SSZ-13 Catalysts for NO_x Reduction by NH₃

Effect of Potassium on the Performance of a CuSO<sub>4</sub>/TiO<sub>2</sub> Catalyst Used in the Selective Catalytic Reduction of NO<sub><i>x</i></sub> by NH<sub>3</sub>

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Regeneration of sulfur-poisoned Cu-SSZ-13 catalysts: Copper speciation and catalytic performance evaluation

Cited by 25 publications

References 48 publications

Impact of Biodiesel-Based Phosphorus and Sulfur on Copper Speciation of Cu-SSZ-13 Catalysts: XAFS Scanning during H2-TPR

Impact of Biodiesel-Based Phosphorus and Sulfur on Copper Speciation of Cu-SSZ-13 Catalysts: XAFS Scanning during H2-TPR

Promotion Effect of Fe Species on SO2 Resistance of Cu-SSZ-13 Catalysts for NOx Reduction by NH3

Effect of Potassium on the Performance of a CuSO<sub>4</sub>/TiO<sub>2</sub> Catalyst Used in the Selective Catalytic Reduction of NO<sub><i>x</i></sub> by NH<sub>3</sub>

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Impact of Biodiesel-Based Phosphorus and Sulfur on Copper Speciation of Cu-SSZ-13 Catalysts: XAFS Scanning during H₂-TPR

Impact of Biodiesel-Based Phosphorus and Sulfur on Copper Speciation of Cu-SSZ-13 Catalysts: XAFS Scanning during H₂-TPR

Promotion Effect of Fe Species on SO₂ Resistance of Cu-SSZ-13 Catalysts for NO_x Reduction by NH₃