Catalytic dehydrofluorination of 1,1,1,2-tetrafluoroethane to synthesize trifluoroethylene over a modified NiO/Al<sub>2</sub>O<sub>3</sub> catalyst

Jia, Wenzhi; Lang, Xuewei; Hu, Chao; Li, Junhui

doi:10.1039/c5cy00211g

Cited by 37 publications

(19 citation statements)

References 30 publications

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“…The results of NH 3 TPD and CO 2 TPD (Figure and Table S2) also reveal that the fluorinated MgO exhibits weaker acidity/basicity than MgO, but its amounts of acid/base sites are bigger than those of MgO. Furthermore, the pyridine IR spectra (Figure S4) confirm the existence of many Lewis acid sites on the fluorinated MgO, shown by the vibration bands at 1446 and 1606 cm −1 , whereas the MgO possesses very few Lewis acid sites. Wojciechowska et al .…”

Section: Resultsmentioning

confidence: 72%

“…Nevertheless, as seen in the conversion of HCFC‐244bb, the fluorinated MgO displayed the highest selectivity for dehydrofluorination among the tested catalyst, whereas MgO displayed high dehydrochlorination selectivity. Several groups have reported that surface Lewis acid sites are related with the dehydrofluorination process . Consequently, the Lewis acid sites of the catalyst play a key role for dehydrofluorination of HCFC‐244bb.…”

Section: Resultsmentioning

confidence: 99%

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Highly Selective Dehydrochlorination of 1,1,1,2‐Tetrafluoro‐2‐chloropropane to 2,3,3,3‐Tetrafluoropropene over Alkali Metal Fluoride Modified MgO Catalysts

et al. 2017

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Gas‐phase selective dehydrochlorination of 1,1,1,2‐tetrafluoro‐2‐chloropropane (HCFC‐244bb) to 2,3,3,3‐tetrafluoropropene was investigated over various K and Cs halides modified MgO catalysts. The reaction proceeded in the absence of additives such as air and HF. High dehydrochlorination selectivity (>97 %) with moderate activity (>14 μmol h−1 m−2) was achieved on KF and CsF modified MgO catalysts, in which the dehydrofluorination process was inhibited. Compared with alkali metal modified MgO, the dehydrofluorination product, 2‐chloro‐3,3,3‐trifluoropropene increased over Zr and Al modified MgO and fluorinated MgO catalysts (sel. of 20–76 %). XRD and energy‐dispersive‐spectrometry results revealed that surface chlorination and fluorination occurred on the MgO‐based catalysts during the reaction. Introducing alkali metal fluorides into the catalyst can reduce the fluorination of MgO and the deposition of chlorine species, thus improving the dehydrochlorination activity and stability of MgO. The NH3 temperature‐programmed desorption (TPD) results show that decreasing the surface acidity of catalyst benefits the dehydrochlorination of HCFC‐244bb, whereas the relationship between the basicity of the catalyst and its dehydrohalogenation behavior is complicated as shown by the CO2 TPD results. According to the hard–soft acid–base principle, the dehydrohalogenation selectivity can be correlated with the surface chemical hardness of the catalyst.

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Section: Resultsmentioning

confidence: 72%

Section: Resultsmentioning

confidence: 99%

Highly Selective Dehydrochlorination of 1,1,1,2‐Tetrafluoro‐2‐chloropropane to 2,3,3,3‐Tetrafluoropropene over Alkali Metal Fluoride Modified MgO Catalysts

et al. 2017

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“…The metal modification on catalysts is an effective method to improve the catalytic performance including the aim product selectivity . The AC−H catalysts were modified by impregnation of K and used to catalytic pyrolysis of HCFC‐142 to synthesize VDF at 600 °C.…”

Section: Resultsmentioning

confidence: 99%

Catalytic Pyrolysis of 2‐Chloro‐1,1‐difluoroethane to Synthesize Vinylidene Fluoride over the Potassium‐Promoted Carbon Catalysts

Yuan

Hong

et al. 2020

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Vinylidene fluoride (VDF) is a crucial monomer for manufacturing polyvinyl fluoride. Catalytic pyrolysis is an ideal route to dispose of 2‐chloro‐1,1‐difluoroethane (HCFC‐142) byproduct derived from the industrial manufacture of 1‐chloro‐1,1‐difluoroethane (HCFC‐142b). The activated carbon catalysts treated by nitric acid and further supported by potassium, were employed to catalytic pyrolysis of HCFC‐142 to synthesize VDF. The prepared K/C catalysts were characterized by BET, X‐ray diffraction (XRD), SEM‐EDX, Raman, NH3‐ and CO2‐ Temperature Programmed Desorption (TPD). With the increase of potassium loading, the surface areas of K/C catalysts reduce gradually, whereas their amounts of surface base sites increase. When the potassium loading reaches up to 1.0%, the 1 K/C catalyst possesses the superior catalytic performance, with the highest conversion of 47.7% and selectivity to VDF of 48.4% at 600 °C. The potassium species improved the catalytic performance of activated carbon is associated with the suitable amounts of surface base sites.

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“…A facile sol‐gel synthesis of nano α‐AlF 3 , which can improve the thermostability of AlF 3 , and show highly active catalyst for dehydrofluorination of hydrofluorocarbons due to the large Lewis acidic amounts . Han et al reported the combustion synthesis for amorphous Al and Cr composite, and as a stable catalyst for dehydrofluorination of 1, 1‐difluoroethane during 60 h, the interaction between Cr species and Al species provides relatively high amount of defect and is favorable for the formation active species. Wang et al prepared the supported Pd/AlF 3 catalyst and found that the addition of Pd significantly improved the stability of AlF 3 catalyst due to Pd additive could effectively pyrolyse carbon deposit .…”

Section: Introductionmentioning

confidence: 99%

A Novel Ni/NiF₂‐AlF₃ Catalyst with Mild‐Strength Lewis Acid Sites for Dehydrofluorination of 1, 1, 1, 2‐Tetrafluoroethane to Synthesize Trifluoroethylene

Liu

et al. 2019

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A novel Ni/NiF2‐AlF3 catalyst was prepared by impregnation and following vapor hydrofluorination, and it was used to dehydrofluorination of tetrafluoroethane to trifluoroethylene. BET, SEM, XRD, XPS, NH3‐TPD and Py‐IR techniques were employed to characterize the Ni/NiF2‐AlF3 catalysts. Based on the NH3‐TPD results, it was interestingly found that the strong acidic sites of Ni/NiF2‐AlF3 catalyst transformed into the mid‐strength acidic sites with the increase of Ni loading, attributing to the roles of Ni on the catalyst surface. Compared with the NiF2‐AlF3 catalyst, the added Ni particles can improve the catalyst activity and stability for dehydrofluorination of 1, 1, 1, 2‐tetrafluoroethane. The best performance was obtained at Al/Ni=2 over the Ni/NiF2‐AlF3 catalyst, with high trifluoroethylene selectivity(99%) and CF3CFH2 conversion of 21.3%, after the reaction for 20 h on‐time stream at 500 °C, which showed the better application possibility as a heterogeneous dehydrofluorination catalyst. It was suggested that catalytic performance was related with the mid‐strength Lewis acidity on the catalyst surface. And the Ni/NiF2‐AlF3 catalyst (Al/Ni=2) possessed the good catalytic stability due to the mild‐strength Lewis acid sites.

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Catalytic dehydrofluorination of 1,1,1,2-tetrafluoroethane to synthesize trifluoroethylene over a modified NiO/Al₂O₃ catalyst

Abstract: The close linear relationship between Lewis acid sites and catalytic activity for the dehydrofluorination of CF3CFH2.

Cited by 37 publications

References 30 publications

Highly Selective Dehydrochlorination of 1,1,1,2‐Tetrafluoro‐2‐chloropropane to 2,3,3,3‐Tetrafluoropropene over Alkali Metal Fluoride Modified MgO Catalysts

Highly Selective Dehydrochlorination of 1,1,1,2‐Tetrafluoro‐2‐chloropropane to 2,3,3,3‐Tetrafluoropropene over Alkali Metal Fluoride Modified MgO Catalysts

Catalytic Pyrolysis of 2‐Chloro‐1,1‐difluoroethane to Synthesize Vinylidene Fluoride over the Potassium‐Promoted Carbon Catalysts

A Novel Ni/NiF₂‐AlF₃ Catalyst with Mild‐Strength Lewis Acid Sites for Dehydrofluorination of 1, 1, 1, 2‐Tetrafluoroethane to Synthesize Trifluoroethylene

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Catalytic dehydrofluorination of 1,1,1,2-tetrafluoroethane to synthesize trifluoroethylene over a modified NiO/Al2O3 catalyst

Abstract: The close linear relationship between Lewis acid sites and catalytic activity for the dehydrofluorination of CF3CFH2.

Cited by 37 publications

References 30 publications

Highly Selective Dehydrochlorination of 1,1,1,2‐Tetrafluoro‐2‐chloropropane to 2,3,3,3‐Tetrafluoropropene over Alkali Metal Fluoride Modified MgO Catalysts

Highly Selective Dehydrochlorination of 1,1,1,2‐Tetrafluoro‐2‐chloropropane to 2,3,3,3‐Tetrafluoropropene over Alkali Metal Fluoride Modified MgO Catalysts

Catalytic Pyrolysis of 2‐Chloro‐1,1‐difluoroethane to Synthesize Vinylidene Fluoride over the Potassium‐Promoted Carbon Catalysts

A Novel Ni/NiF2‐AlF3 Catalyst with Mild‐Strength Lewis Acid Sites for Dehydrofluorination of 1, 1, 1, 2‐Tetrafluoroethane to Synthesize Trifluoroethylene

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Catalytic dehydrofluorination of 1,1,1,2-tetrafluoroethane to synthesize trifluoroethylene over a modified NiO/Al₂O₃ catalyst

A Novel Ni/NiF₂‐AlF₃ Catalyst with Mild‐Strength Lewis Acid Sites for Dehydrofluorination of 1, 1, 1, 2‐Tetrafluoroethane to Synthesize Trifluoroethylene